Hydroxy resin, styrene resin, method for producing hydroxy resin, method for producing styrene resin, and applications thereof

Abstract

To provide a styrene resin having excellent low dielectric properties and excellent thermal resistance.SOLUTION: Provided is a hydroxy resin represented by Formula (T-OH) and having a number average molecular weight of 850 to 4000. In Formula (T-OH), R is a group containing structural units represented by Formula (Tx-OH).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a hydroxy resin, a styrene resin, a method for producing a hydroxy resin, a method for producing a styrene resin, a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device. [Background technology]

[0002] In recent years, there has been an accelerating trend toward higher integration and finer design of semiconductor elements used in mobile terminals, electronic devices, communication devices, etc. Accordingly, there is a demand for technology that enables high-density mounting of semiconductor elements, and there is also a demand for improvements in printed wiring boards, which play an important role in such mounting. On the other hand, the applications of electronic devices are becoming more diverse and expanding. In response to this, the properties required for printed wiring boards, metal foil-clad laminates, prepregs, etc. used therein are also becoming more diverse and stricter. In order to obtain improved printed wiring boards while taking into account such required properties, various materials and processing methods have been proposed. One of these is the improvement and development of the resin materials that make up prepregs and resin composite sheets.

[0003] For example, Patent Document 1 discloses a resin as such an electronic material. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-172242 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, the hydroxy resin described in Patent Document 1 can be used as a raw material for electronic materials. However, the present inventors have found that the styrene resin obtained from the hydroxy resin described in Patent Document 1 has poor low dielectric properties (Dk and / or Df) when cured. The present invention aims to solve such problems and to obtain a styrene resin capable of providing a cured product having excellent low dielectric properties (Dk and / or Df) and excellent heat resistance. It is also an object of the present invention to provide a hydroxyl resin which is a raw material of the styrene resin, a method for producing the hydroxyl resin, a method for producing the styrene resin, and a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device using the styrene resin. [Means for solving the problem]

[0006] As described above, when a styrene resin is produced from the hydroxy resin described in Patent Document 1, the cured product of the styrene resin is inferior in low dielectric properties (Dk and / or Df), and it is difficult to use the styrene resin as an electronic material. The present inventors have investigated the reason for this and speculated that the hydroxy resin described in Patent Document 1 has a small molecular weight. That is, Patent Document 1 discloses a hydroxy resin having an average number (n) of repeating units containing an indane skeleton of 2.3 in an example of the same document. This results in a number average molecular weight of about 766. That is, the molecular weight is small, and the proportion of indane skeletons in the resin is low. Therefore, it was speculated that the low dielectric properties (Dk and / or Df) of the cured product of the styrene resin obtained using the hydroxy resin is inferior. Furthermore, in this embodiment, as described in detail below, by removing the excess styrene compound reacted with the hydroxyl resin, the low dielectric properties (Dk and / or Df) of the resulting cured product can be further improved.

[0007] Under these circumstances, the above problems were solved by the following means. <1> A hydroxy resin represented by the formula (T-OH) and having a number average molecular weight of 850 to 4,000. [ka] (In formula (T-OH), R is a group containing a structural unit represented by formula (Tx-OH). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y is independently an integer of 0 to 4.) [ka] (In formula (Tx-OH), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. The structural units (a), (b), and (c) are each bonded to the structural units (a), (b), and (c) or other groups at *, and each structural unit may be bonded randomly.) <2> The number average molecular weight is 900 to 2500. <1> The hydroxy resin according to claim 1. <3> Formula (T-OH) is represented by formula (T-OH2): <1> or <2> The hydroxy resin according to claim 1. [ka] (In formula (T-OH2), R is a group containing a structural unit represented by formula (Tx-OH). Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y independently represent an integer of 0 to 4.) [ka] (In formula (Tx-OH), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. The structural units (a), (b), and (c) are each bonded to the structural units (a), (b), and (c) or other groups at *, and each structural unit may be bonded randomly.) <4> A styrene resin represented by the formula (T-St) and having a number average molecular weight of 1,050 to 4,000. [ka] (In formula (T-St), R is a group containing a structural unit represented by formula (Tx-St). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each Mc is independently a hydrocarbon group having 1 to 12 carbon atoms. Each x, y, and z is independently an integer of 0 to 4. r is an integer of 1 to 6. R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. [ka] (In formula (Tx-St), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. The structural units (a), (b), and (c) are each bonded to the structural units (a), (b), and (c) or other groups at *, and each structural unit may be bonded randomly.) <5> Formula (T-St) is represented by formula (T-St2), <4> The styrene resin according to claim 1. [ka] (In formula (T-St2), R is a group containing a structural unit represented by formula (Tx-St). Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms. Each x, y, and z independently represent an integer of 0 to 4. r represents an integer of 1 to 6. R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. [ka] (In formula (Tx-St), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p are each independently a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x is an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.) <6> The number average molecular weight is 1050 to 2500. <4> or <5> The styrene resin according to claim 1. <7> The sum of the total chlorine content and the total bromine content is 2500 mass ppm or less. <4> ~ <6> 13. The styrene resin according to claim 12, <8> The dielectric tangent of the cured product of the styrene resin at a frequency of 10 GHz is 0.0030 or less. <4> ~ <7> 13. The styrene resin according to claim 12, <9> Using a resin (T), The resin (T) is a resin represented by the formula (T): <1> ~ <3> 13. A method for producing a hydroxy resin according to claim 12. [ka] (In formula (T), R is a group containing a structural unit represented by formula (Tx). Ma represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer of 0 to 4.) [ka] (In formula (Tx), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.) <10> The resin (T) is reacted with a compound represented by formula (P), <9> A method for producing the hydroxy resin according to claim 1. [ka] (In formula (P), each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. y is an integer of 0 to 4.) <11> The compound represented by formula (P) includes a compound represented by formula (P1). <10> A method for producing the hydroxy resin according to claim 1. [ka] (In formula (P1), each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom; and y represents an integer of 0 to 4.) <12> When the compound represented by formula (P) is reacted with the resin (T), the total content of m-bis(α-hydroxyisopropyl)benzene, p-bis(α-hydroxyisopropyl)benzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene in the reaction system is 10 mass% or less based on the amount of the resin (T). <10> or <11> A method for producing the hydroxy resin according to claim 1. <13> <1> ~ <3> The hydroxy resin according to any one of the above claims is used. <4> ~ <8> 13. The method for producing a styrene resin according to claim 12, <14> reacting the hydroxy resin with a compound represented by formula (S), <13> A method for producing a styrene resin according to claim 1. [ka] (In formula (S), Hr represents a chlorine atom or a bromine atom. Mc represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6. R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. <15> <4> ~ <8> A resin composition comprising the styrene resin according to any one of claims 1 to 5. <16> <15> A cured product of the resin composition described above. <17> A substrate; <15> A prepreg formed from the resin composition according to claim 1. <18> <17> 13. A metal foil-clad laminate comprising: at least one layer formed from the prepreg according to claim 12; and metal foil disposed on one or both sides of the layer formed from the prepreg. <19> A support and a substrate disposed on the surface of the support. <15> and a layer formed from the resin composition according to claim 1. <20> A printed wiring board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, the insulating layer comprising: <15> A layer formed from the resin composition according to <17> A printed wiring board comprising at least one layer formed from the prepreg according to claim 1. <21> <20> A semiconductor device comprising the printed wiring board according to claim 1. Effect of the Invention

[0008] The present invention makes it possible to obtain a styrene resin capable of providing a cured product having excellent low dielectric properties (Dk and / or Df) and excellent heat resistance. Furthermore, the present invention makes it possible to provide a hydroxyl resin, which is a raw material for the styrene resin, a method for producing the hydroxyl resin, a method for producing the styrene resin, and a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device using the styrene resin. [Brief description of the drawings]

[0009] [Figure 1] 1 shows an NMR chart of the hydroxy resin (C) synthesized in Example 3. [Diagram 2] 1 shows an NMR chart of the styrene resin (C) synthesized in Example 3. [Diagram 3] 1 shows a GPC chart of the styrene resin (C) synthesized in Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. In this specification, the use of "to" means that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical properties and characteristic values ​​are those at 23° C. unless otherwise specified. In the description of groups (atomic groups) in this specification, when the description does not indicate whether the group is substituted or unsubstituted, the description also includes groups (atomic groups) that have a substituent as well as groups (atomic groups) that have no substituent. For example, the term "alkyl group" includes not only alkyl groups that have no substituent (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, when the description does not indicate whether the group is substituted or unsubstituted, the description is preferably unsubstituted. In this specification, the (meth)allyl group refers to both or either of allyl and methallyl, "(meth)acrylate" refers to both or either of acrylate and methacrylate, "(meth)acryl" refers to both or either of acryl and methacryl, and "(meth)acryloyl" refers to both or either of acryloyl and methacryloyl. In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2022, unless otherwise stated.

[0011] In this specification, the resin solids refers to components excluding fillers and solvents, and is intended to include styrene resin, other thermosetting compounds that are blended as necessary, and other resin additive components (additives such as flame retardants, etc.). In this specification, the terms relative permittivity and dielectric constant are used interchangeably.

[0012] <Hydroxy resin> The hydroxyl resin of the present embodiment is represented by the formula (T-OH) and is characterized by having a number average molecular weight of 850 to 4,000. [ka] (In formula (T-OH), R is a group containing a structural unit represented by formula (Tx-OH). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y is independently an integer of 0 to 4.) [ka] (In formula (Tx-OH), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.)

[0013] In formula (T-OH), R is a group containing a structural unit represented by formula (Tx-OH). In the formula (Tx-OH), n, o and p each represent the average number of repeating units in all molecules in the resin. In formula (Tx-OH), the sum of n, o, and p is preferably 1.1≦n+o+p, more preferably 1.2≦n+o+p, even more preferably 1.5≦n+o+p, still more preferably 2.0≦n+o+p, even more preferably 2.5≦n+o+p, still more preferably 3.0≦n+o+p, particularly preferably 3.3≦n+o+p, and furthermore, more preferably 3.5≦n+o+p, 3.7≦n+o+p, 4.0≦n+o+p, 4.2≦n+o+p in this order. In formula (Tx-OH), the sum of n, o and p is preferably n+o+p≦20.0, more preferably n+o+p≦10.0, even more preferably n+o+p≦8.0, even more preferably n+o+p≦7.0, even more preferably n+o+p≦6.8, and even more preferably n+o+p≦6.5. The sum of n, o and p can be calculated by the method described in the examples below.

[0014] In formula (Tx-OH), Ma each independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, and each independently is preferably a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, more preferably a hydrocarbon group having 1 to 5 carbon atoms which may be substituted with a halogen atom, and further preferably a hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a halogen atom. Examples of halogen atoms include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom or a chlorine atom is preferable. Each independently is preferably a hydrocarbon group having 1 to 12 carbon atoms which is not substituted with a halogen atom. The hydrocarbon group is preferably an alkyl group, and more preferably a linear alkyl group. Ma is particularly preferably a methyl group or an ethyl group.

[0015] In formula (Tx-OH), x represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and even more preferably 0.

[0016] In formula (T-OH), each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring, preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. When Arm is a benzene ring and y is an integer of 1 to 4, it is preferable that the OH group bonded to Arm and Mb are bonded at one or two of the ortho and para positions (preferably at least one or two of the ortho positions). In formula (T-OH), each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, and has the same meaning as Ma in formula (Tx-OH), and the preferred range is also the same. In the formula (T-OH), Mb each independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom, and is preferably a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and more preferably a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alicyclic alkyl group having 4 to 8 carbon atoms, a cumyl group, a phenyl group, or a benzyl group. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferred, and a fluorine atom or a chlorine atom is more preferred. As the linear or branched alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, an octyl group, or a nonyl group is preferred. As the alicyclic alkyl group having 4 to 8 carbon atoms, a cyclohexyl group is preferred. In this embodiment, Mb is more preferably a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a benzyl group, and more preferably a hydroxyl group, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, or a benzyl group.

[0017] In formula (T-OH), x independently represents an integer of 0 to 4 and has the same meaning as x in formula (Tx-OH), and the preferred range is also the same. In formula (T-OH), each y independently represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

[0018] The formula (T-OH) is preferably represented by the formula (T-OH2). [ka] (In formula (T-OH2), R is a group containing a structural unit represented by formula (Tx-OH). Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y independently represent an integer of 0 to 4.) [ka] (In formula (Tx-OH), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.)

[0019] In formula (T-OH2), R, Ma, Mb, x, and y have the same meanings as R, Ma, Mb, x, and y in formula (T-OH), respectively, and the preferred ranges are also the same. In formula (T-OH2), when y is an integer of 1 to 4, it is preferable that the OH group bonded to the benzene ring and Mb are bonded at one or two of the ortho and para positions (preferably at least one or two of the ortho positions).

[0020] Furthermore, the hydroxy resin of the present embodiment preferably has a parameter α calculated from the formula (α) of 0.55 or more and 1.00 or less.

number

[0021] The parameter α in the hydroxy resin is preferably 0.57 or more, more preferably 0.59 or more, even more preferably 0.60 or more, even more preferably 0.62 or more, and may be 0.63 or more, 0.65 or more, 0.70 or more, 0.75 or more, or 0.80 or more. By making it equal to or more than the lower limit, the low dielectric properties (low relative dielectric constant and / or low dielectric tangent) and heat resistance tend to be further improved when the hydroxy group is converted to a styrene group. Since the parameter α tends to be substantially excellent in low dielectric properties and heat resistance, the parameter α is preferably large, but may be 0.95 or less, 0.94 or less, 0.93 or less, 0.91 or less, or 0.90 or less.

[0022] The hydroxy resin of the present embodiment has a number average molecular weight of 850 to 4000. By making it equal to or more than the lower limit, the low dielectric properties (Dk and / or Df, especially low dielectric tangent) tend to be improved when the hydroxy group is converted to a styrene group. In addition, by making it equal to or less than the upper limit, the solvent solubility and the moldability and solvent solubility tend to be improved when the hydroxy group is converted to a styrene group. The number average molecular weight of the hydroxy resin is preferably 900 or more, more preferably 950 or more, even more preferably 1000 or more, even more preferably 1050 or more, and may be 1100 or more, 1150 or more, 1200 or more, 1250 or more, or 1300 or more. The number average molecular weight of the hydroxy resin is also preferably 4000 or less, more preferably 3000 or less, even more preferably 2700 or less, even more preferably 2500 or less, even more preferably 2300 or less, 2200 or less, or 2100 or less, and even more preferably 2000 or less, 1900 or less, or 1800 or less, and even more preferably 1700 or less, 1600 or less, or 1500 or less.

[0023] The weight average molecular weight of the hydroxy resin of this embodiment is preferably 1000 or more, more preferably 1100 or more, even more preferably 1200 or more, even more preferably 1350 or more, even more preferably 1450 or more, even more preferably 1500 or more, and may be 1550 or more, 1600 or more, 1650 or more, 1700 or more, 1750 or more, or 1800 or more. By making it equal to or greater than the lower limit, the low dielectric properties (Dk and / or Df, especially low dielectric tangent) tend to be improved when the hydroxy group is converted to a styrene group. The weight average molecular weight of the hydroxy resin is also preferably 5000 or less, more preferably 4000 or less, even more preferably 3000 or less, even more preferably 2500 or less, even more preferably 2400 or less, and even more preferably 2300 or less. By making it equal to or less than the upper limit, the solvent solubility and the moldability and solvent solubility when the hydroxy group is converted to a styrene group tend to be improved.

[0024] The dispersity (Mw / Mn) of the hydroxy resin of this embodiment is preferably 1.20 or more, more preferably 1.22 or more, even more preferably 1.25 or more, still more preferably 1.30 or more, and even more preferably 1.32 or more. The dispersity (Mw / Mn) of the hydroxy resin is preferably 2.00 or less, more preferably 1.90 or less, even more preferably 1.80 or less, still more preferably 1.70 or less, and even more preferably 1.60 or less.

[0025] The hydroxyl equivalent of the hydroxyl resin of this embodiment is preferably 365 g / eq. or more, more preferably 400 g / eq. or more, even more preferably 450 g / eq. or more, even more preferably 500 g / eq. or more, even more preferably 550 g / eq. or more, and further preferably 570 g / eq. or more, 600 g / eq. or more, 650 g / eq. or more, 660 g / eq. or more, 670 g / eq. or more, 680 g / eq. or more, 700 g / eq. or more, 750 g / eq. or more, and 800 g / eq. or more in this order. By making it equal to or more than the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) when the hydroxyl group is converted to a styrene group tend to be lowered. The hydroxyl group equivalent of the hydroxyl resin is preferably 2000 g / eq or less, more preferably 1500 g / eq or less, even more preferably 1400 g / eq or less, even more preferably 1200 g / eq or less, even more preferably 1000 g / eq or less, and may be 900 g / eq or less. By making it equal to or less than the upper limit, the solvent solubility and the moldability and solvent solubility when the hydroxyl group is converted to a styrene group tend to be further improved. The hydroxyl group equivalent of the hydroxyl resin of the present embodiment is measured according to the method described in the Examples section below.

[0026] <Styrene resin> The styrene resin of the present embodiment is represented by the formula (T-St) and has a number average molecular weight of 1,050 to 4,000. [ka] (In formula (T-St), R is a group containing a structural unit represented by formula (Tx-St). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each Mc is independently a hydrocarbon group having 1 to 12 carbon atoms. Each x, y, and z are independently an integer of 0 to 4. r is an integer of 1 to 6. R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. [ka] (In formula (Tx-St), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p are each independently a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x is an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.)

[0027] In formula (T-St), R is a group containing a structural unit represented by formula (Tx-St). In formula (Tx-St), n, o and p each represent the average number of repeating units in all molecules in the resin. In formula (Tx-St), the sum of n, o, and p is preferably 1.1≦n+o+p, more preferably 1.2≦n+o+p, even more preferably 1.5≦n+o+p, still more preferably 2.0≦n+o+p, even more preferably 2.5≦n+o+p, still more preferably 3.0≦n+o+p, particularly preferably 3.3≦n+o+p, and furthermore, more preferably 3.5≦n+o+p, 3.7≦n+o+p, 4.0≦n+o+p, 4.2≦n+o+p in this order. In formula (Tx-St), the sum of n, o and p is preferably n+o+p≦20.0, more preferably n+o+p≦10.0, even more preferably n+o+p≦8.0, even more preferably n+o+p≦7.0, even more preferably n+o+p≦6.5, and even more preferably n+o+p≦6.4. The sum of n, o and p can be calculated by the method described in the examples below. In addition, the sum of n, o and p in formula (Tx-St) is usually the same as the sum of n, o and p in formula (Tx).

[0028] In formula (Tx-St), Ma and x have the same meanings as Ma and x in formula (Tx-OH), respectively, and the preferred ranges are also the same.

[0029] In formula (T-St), each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring, and has the same meaning as Arm in formula (T-OH), and the preferred range is also the same. In formula (T-St), each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, and has the same meaning as Ma in formula (Tx-St), and the preferred range is also the same. In formula (T-St), Mb each independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom, and has the same meaning as Mb in formula (T-OH), and the preferred range is also the same.

[0030] In formula (T-St), each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, further preferably a methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, octyl group, or nonyl group, and still more preferably a methyl group, ethyl group, isopropyl group, isobutyl group, or t-butyl group.

[0031] In formula (T-St), x and y have the same meanings as x and y in formula (T-OH), and the preferred ranges are also the same. In formula (T-St), each z independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and most preferably 0. In formula (T-St), r represents an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and even more preferably 1. In the formula (T-St), R 1 , R 2 , and R 3 R each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom. 1 , R 2 , and R 3 The number of carbon atoms in the alkyl group, alkenyl group or alkynyl group is preferably 5 or less, and more preferably 3 or less.

[0032] In this embodiment, the formula (T-St) is preferably represented by the formula (T-St2). [ka] (In formula (T-St2), R is a group containing a structural unit represented by formula (Tx-St). Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms. Each x, y, and z independently represent an integer of 0 to 4. r represents an integer of 1 to 6. R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. [ka] (In formula (Tx-St), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p are each independently a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x is an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.)

[0033] In formula (T-St2), R, Ma, Mb, Mc, x, y, z, r, R 1 , R 2 , and R 3 are R, Ma, Mb, Mc, x, y, z, r, and R in formula (T-St), respectively. 1 , R 2 , and R 3 The same definition and preferred range are also the same.

[0034] Furthermore, the styrene resin of the present embodiment preferably has a parameter α calculated from the formula (α) of 0.55 or more and 1.00 or less.

number

[0035] The parameter α in the styrene resin is preferably 0.57 or more, more preferably 0.59 or more, even more preferably 0.60 or more, even more preferably 0.62 or more, and may be 0.65 or more, 0.70 or more, 0.75 or more, or 0.80 or more. By making it equal to or more than the lower limit, the low dielectric properties (low relative dielectric constant and / or low dielectric tangent) and heat resistance of the obtained cured product tend to be improved. Since the low dielectric properties and heat resistance of the obtained cured product tend to be excellent, the parameter α is preferably large, but may be 0.95 or less, 0.94 or less, 0.93 or less, or 0.92 or less.

[0036] The number average molecular weight of the styrene resin of the present embodiment is 1050 to 4000. By making it equal to or more than the lower limit, the low dielectric properties (Dk and / or Df, particularly low dielectric tangent) of the obtained cured product tend to be improved. This is thought to be due to the fact that the proportion of the indane skeleton (structural unit (a) in formula (Tx-St)) in the molecule increases by increasing the molecular weight. In addition, by making it equal to or less than the upper limit, the moldability and solvent solubility tend to be improved. The number average molecular weight of the styrene resin is preferably 1100 or more, more preferably 1150 or more, even more preferably 1200 or more, even more preferably 1250 or more, even more preferably 1280 or more, and may be 1300 or more, 1400 or more, 1500 or more, 1550 or more, or 1590 or more. The number average molecular weight of the styrene resin is preferably 3,000 or less, more preferably 2,500 or less, even more preferably 2,000 or less, even more preferably 1,800 or less, and even more preferably 1,700 or less.

[0037] The styrene resin of the present embodiment preferably has a weight average molecular weight of 1200 or more, more preferably 1250 or more, even more preferably 1300 or more, even more preferably 1400 or more, and further preferably 1500 or more, 1550 or more, 1600 or more, 1650 or more, 1700 or more, 1750 or more, 1790 or more, 1810 or more, 2050 or more, and 2250 or more in this order. By making it equal to or greater than the lower limit, the low dielectric properties (Dk and / or Df, particularly low dielectric tangent) of the obtained cured product tend to be further improved. The weight average molecular weight of the styrene resin is preferably 5000 or less, more preferably 4000 or less, even more preferably 3000 or less, even more preferably 2800 or less, and even more preferably 2500 or less. By making it equal to or less than the upper limit, the moldability and solvent solubility tend to be further improved.

[0038] The polydispersity (Mw / Mn) of the styrene resin used in this embodiment is preferably 1.18 or more, more preferably 1.20 or more, even more preferably 1.25 or more, still more preferably 1.30 or more, even more preferably 1.32 or more, and may be 1.34 or more. The polydispersity (Mw / Mn) of the styrene resin is preferably 2.00 or less, more preferably 1.85 or less, even more preferably 1.70 or less, even more preferably 1.60 or less, and even more preferably 1.50 or less.

[0039] In this embodiment, the total amount of chlorine and bromine in the styrene resin is small. Carbon atoms and chlorine atoms or bromine atoms are strongly polarized, so by reducing the molecules having these halogen atoms, the polarization within the molecule can be suppressed, and the low dielectric properties (Dk and / or Df) of the resulting cured product can be achieved, and the low dielectric properties can be further improved. In addition, if the resin contains a large amount of hydrolyzable chlorine and bromine-containing compounds, they tend to hydrolyze upon moisture absorption, liberating chlorine ions and bromine ions, which deteriorates the migration properties, but by reducing the molecules having these halogen atoms, the migration properties can be improved. From the above viewpoint, more specifically, the sum of the total chlorine amount and the total bromine amount in the styrene resin is preferably 2500 mass ppm or less, more preferably 2000 mass ppm or less, even more preferably 1500 mass ppm or less, even more preferably 1000 mass ppm or less, even more preferably 500 mass ppm or less, even more preferably 450 mass ppm or less, and particularly more preferably 400 mass ppm or less. In addition, the lower limit of the sum of the total chlorine amount and the total bromine amount in the styrene resin is ideally 0 mass ppm, but 10 mass ppm or more is practical, and even if it is 100 mass ppm or more, the required performance is satisfied. In particular, in this embodiment, the amount of chlorine in the styrene resin is preferably 2500 ppm by mass or less, more preferably 2000 ppm by mass or less, even more preferably 1500 ppm by mass or less, even more preferably 1000 ppm by mass or less, even more preferably 500 ppm by mass or less, and particularly more preferably 400 ppm by mass or less. The lower limit of the amount of chlorine in the styrene resin is ideally 0 ppm by mass, but 10 ppm by mass or more is practical, and even if it is 100 ppm by mass or more, the required performance is satisfied.

[0040] Such a styrene resin having few chlorine atoms and bromine atoms can be achieved, for example, by removing low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms, in particular, compounds represented by formula (S) and impurities of compounds represented by formula (S), in the production method of a styrene resin described below. The impurities of the compound represented by formula (S) include compounds in which the α- or β-carbon of the compound represented by formula (S) is substituted with a chlorine atom or a bromine atom, and dichloro- or dibromo-substituted compounds of the compound represented by formula (S). More specifically, the following compounds can be mentioned. [ka]

[0041] The styrene resin of this embodiment has a hydroxyl equivalent of preferably 13000g / eq. or more, more preferably 15000g / eq. or more, even more preferably 20000g / eq. or more, even more preferably 30000g / eq. or more, even more preferably 35000g / eq. or more, even more preferably 40000g / eq., even more preferably 60000g / eq. or more, and particularly preferably 80000g / eq. or more. By setting it to the lower limit or more, the relative dielectric constant (Dk) and dielectric loss tangent (Df) tend to be lower. The upper limit of the hydroxyl amount is not particularly specified, but for example, 100000g / eq. or less is practical. The hydroxyl equivalent in the styrene resin is measured according to the description in the Examples section below.

[0042] The styrene resin of this embodiment has a low dielectric loss tangent when cured. Specifically, the dielectric loss tangent of the cured product of the styrene resin of this embodiment at a frequency of 10 GHz is preferably 0.0030 or less, more preferably 0.0028 or less, even more preferably 0.0025 or less, even more preferably 0.0023 or less, even more preferably 0.0021 or less, and may be 0.0019 or less, 0.0018 or less, 0.0017 or less, 0.0016 or less, or 0.0015 or less. The lower limit of the dielectric loss tangent is ideally 0, but is practically 0.0001 or more. The styrene resin of this embodiment has a low dielectric constant when cured. Specifically, the dielectric constant of the cured product of the styrene resin of this embodiment at a frequency of 10 GHz is preferably 2.37 or less, more preferably 2.36 or less, even more preferably 2.35 or less, even more preferably 2.33 or less, and even more preferably 2.32 or less. The lower limit of the dielectric constant is ideally 0, but practically 0.01 or more. The dielectric loss tangent and the relative dielectric constant of the cured styrene resin are measured according to the method described in the examples below.

[0043] The cured product of the styrene resin of the present embodiment preferably has a high glass transition temperature. Specifically, it is preferably 180° C. or higher, more preferably 200° C. or higher, even more preferably 210° C. or higher, even more preferably 213° C. or higher, and even more preferably 214° C. or higher. There is no particular upper limit to the glass transition temperature, but a temperature of 350° C. or lower is practical. The glass transition temperature of the cured product of the styrene resin is measured according to the method described in the Examples below.

[0044] <Method of manufacturing hydroxy resin> The method for producing a hydroxy resin according to the present embodiment preferably includes the use of a resin (T), which is a resin represented by formula (T), and is preferably a resin represented by formula (T1). [ka] (In formula (T), R is a group containing a structural unit represented by formula (Tx). Ma represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer of 0 to 4.) [ka] (In formula (Tx), n, o, and p represent the average number of repeating units, n represents a number greater than 0 and equal to or less than 20, o and p each independently represent a number from 0 to 20, and 1.0≦n+o+p≦20.0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural units (a), (b), (c), or other groups, and each structural unit may be bonded randomly.) [ka] (In formula (T1), R is a group containing a structural unit represented by formula (Tx).)

[0045] The hydroxy resin obtained by using such a resin (T) is a useful raw material for the styrene resin of this embodiment.

[0046] In formula (T), Ma and x each independently have the same meaning as Ma and x in formula (T-OH), and the preferred ranges are also the same. In formula (Tx), n, o and p each represent the average number of repeating units in all molecules in the resin. In formula (Tx), the sum of n, o, and p is preferably 1.1≦n+o+p, more preferably 1.2≦n+o+p, even more preferably 1.5≦n+o+p, still more preferably 2.0≦n+o+p, even more preferably 2.5≦n+o+p, still more preferably 3.0≦n+o+p, particularly preferably 3.3≦n+o+p, and furthermore, more preferably 3.5≦n+o+p, 3.7≦n+o+p, 4.0≦n+o+p, 4.2≦n+o+p in this order. In the formula (Tx-OH), the sum of n, o and p is preferably n+o+p≦20.0, more preferably n+o+p≦10.0, even more preferably n+o+p≦8.0, even more preferably n+o+p≦7.0, even more preferably n+o+p≦6.5, and even more preferably n+o+p≦6.4. The sum of n, o and p can be calculated by the method described in the Examples below.

[0047] In formula (Tx), Ma and x have the same meanings as Ma and x in formula (Tx-OH), respectively, and the preferred ranges are also the same.

[0048] However, by reacting the resin (T) with the compound represented by formula (P), the molecular weight is improved, and the value of n+o+p tends to be larger. In addition, during the reaction, the structural unit (b) and the structural unit (c) in formula (Tx) become the structural unit (a), so that the proportion of the structural unit (a) in the hydroxyl resin and the styrene resin synthesized using the same tends to be increased. As a result, it is possible to achieve lower Dk and Df.

[0049] The resin represented by formula (T) preferably has a parameter α calculated from formula (α) of 0.55 or more and 1.00 or less, and a parameter β calculated from formula (β) of 0.20 or more and 3.00 or less.

number

[0050] The parameter α in the resin represented by formula (T) is preferably 0.57 or more, more preferably 0.59 or more, even more preferably 0.60 or more, even more preferably 0.62 or more, and may be 0.65 or more, 0.70 or more, 0.75 or more, or 0.80 or more. By making it equal to or more than the lower limit, the heat resistance of the obtained cured product tends to be improved. Since the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product tend to be excellent, the parameter α is preferably large, but may be 0.95 or less, 0.90 or less, 0.85 or less, 0.82 or less, 0.80 or less, 0.77 or less, 0.75 or less, or 0.74 or less. The parameter β is preferably 0.25 or more, more preferably 0.30 or more, even more preferably 0.35 or more, even more preferably 0.40 or more, even more preferably 0.43 or more, even more preferably 0.50 or more, and may be 0.60 or more, 0.65 or more, 0.70 or more, 0.77 or more, 0.80 or more, 0.90 or more, or 0.95 or more. By making it equal to or more than the lower limit, the heat resistance of the obtained cured product tends to be improved and Df tends to be lower. The parameter β is preferably 2.50 or less, more preferably 2.00 or less, even more preferably 1.50 or less, even more preferably 1.30 or less, even more preferably 1.20 or less, even more preferably 1.10 or less, and may be 1.00 or less, 0.95 or less, 0.90 or less, 0.85 or less, 0.83 or less, or 0.80 or less. By ensuring that the content is equal to or less than the upper limit, the heat resistance of the obtained cured product tends to be improved and Df tends to be low.

[0051] The number average molecular weight (Mn) of the resin represented by formula (T) in terms of polystyrene by GPC (gel permeation chromatography) method (details are according to the method described in the examples below) is preferably 400 or more, more preferably 500 or more, even more preferably 550 or more, even more preferably 600 or more, and even more preferably 650 or more. By making it equal to or more than the lower limit, the heat resistance of the obtained cured product tends to be improved and Df tends to be lower. In addition, the upper limit of the number average molecular weight (Mn) of the resin represented by formula (T) in terms of polystyrene by GPC (gel permeation chromatography) method is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, even more preferably 1500 or less, and even more preferably 1250 or less. By making it equal to or less than the upper limit, the heat resistance of the obtained cured product tends to be improved and Df tends to be lower. In addition, the polystyrene-equivalent weight average molecular weight (Mw) of the resin represented by formula (T) by GPC (details are according to the method described in the Examples below) is preferably 500 or more, more preferably 800 or more, even more preferably 900 or more, and even more preferably 1000 or more. By making it equal to or more than the lower limit, the heat resistance of the obtained cured product tends to be improved and Df tends to be lower. The upper limit of the polystyrene-equivalent weight average molecular weight (Mw) of the resin represented by formula (T) by GPC (details are according to the method described in the Examples below) is preferably 6000 or less, more preferably 5000 or less, even more preferably 4000 or less, even more preferably 3000 or less, and even more preferably 2800 or less. By making it equal to or less than the upper limit, the heat resistance of the obtained cured product tends to be improved and Df tends to be lower.

[0052] The Mw / Mn of the resin represented by formula (T) is more preferably 1.2 or more, even more preferably 1.3 or more, even more preferably 1.4 or more, even more preferably 1.5 or more, and even more preferably 1.6 or more. The Mw / Mn of the resin represented by formula (T) is more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and may be 2.0 or less, or may be 1.8 or less. The weight average molecular weight and the number average molecular weight are measured according to the method described in the Examples below.

[0053] The method for producing the resin (T) is not particularly limited, and resins obtained by known production methods can be used. In addition, the raw materials, reaction temperature, catalyst type, catalyst amount, reaction solvent, raw material concentration, etc., used in synthesizing the resin (T) are not particularly limited, and can be appropriately selected or controlled according to the desired physical properties described above.

[0054] Examples of raw materials that can be used in synthesizing the resin (T) include m-bis(α-hydroxyisopropyl)benzene, p-bis(α-hydroxyisopropyl)benzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene.

[0055] The reaction temperature when synthesizing the resin (T) is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher, and may be 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher. By setting the temperature at or above the lower limit, the reaction rate and the ratio of the indane skeleton (structural unit (a) in formula (Tx)) tend to be improved, which is preferable. In addition, the reaction temperature is preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower. By setting the temperature at or below the upper limit, the generation of by-products tends to be effectively suppressed. The reaction temperature does not need to be the same from the start to the end of the reaction, and may be changed. In this case, it is preferable that the average reaction temperature in the entire process is within the above range.

[0056] The catalyst used in synthesizing the resin (T) is not particularly limited, but may be an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, Lewis acids such as BF3 ether complex, BF3 phenol complex, aluminum chloride, zinc chloride, and indium chloride, solid acids such as activated clay, acid clay, silica alumina, and zeolite, heteropolyhydrochloric acid, and strongly acidic ion exchange resins. When a catalyst is used, the amount thereof is, for example, 0.01 to 20.0 parts by mass per 100 parts by mass of the raw materials for the resin (T). The catalyst is usually one type alone, but two or more types may be used in combination. When using a combination of catalysts, it is preferable that the total amount is within the above range.

[0057] The reaction solvent used in synthesizing the resin (T) is not particularly limited, but may be an aromatic hydrocarbon solvent such as toluene, benzene, chlorobenzene, or xylene, a halogenated hydrocarbon solvent such as methylene chloride or chloroform, an aliphatic hydrocarbon solvent such as hexane or heptane, an ester solvent such as ethyl acetate or propyl acetate, an amide solvent such as dimethylformamide or dimethylacetamide, an alcohol solvent, or a ketone solvent, or water may be added. Examples of the alcohol solvent include methanol, ethanol, butanol, propanol, methylpropylene diglycol, diethylene glycol ethyl ether, butylpropylene glycol, and propylpropylene glycol, and examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, and methyl isobutyl ketone, and others include, but are not limited to, tetrahydrofuran and dioxane. An example of the reaction solvent in this embodiment includes an aromatic hydrocarbon solvent.

[0058] The concentration of the above-mentioned raw materials when synthesizing the resin (T) is preferably 5% or more, more preferably 8% or more, and preferably 10% or more, and may be 12% or more, 15% or more, 17% or more, 20% or more, 22% or more, or 25% or more. By making the concentration equal to or greater than the lower limit, the reaction rate and the ratio of the indane skeleton (structural unit (a) in formula (Tx)) tend to be improved, which is preferable. In addition, the concentration of the above-mentioned raw materials is preferably 49% or less, more preferably 40% or less. By making the concentration equal to or less than the upper limit, the generation of by-products tends to be effectively suppressed. In addition, the concentration does not need to be the same from the start to the end of the reaction, and may be changed.

[0059] In the production of the hydroxy resin of this embodiment, it is preferable to include reacting the above-mentioned resin (T) with a compound represented by formula (P). In this embodiment, it is presumed that the proportion of the structural unit (a) in formula (Tx) can be further increased during the addition reaction of the compound represented by formula (P). This is presumed to be because the structural unit (b) and the structural unit (c) in formula (Tx) become the structural unit (a) during the addition reaction. In addition, it is presumed that the cationic polymerization of the resin (T) also proceeds during the addition reaction of the compound represented by formula (P), and the total value of n+o+p in formula (Tx) increases. As a result, it is presumed that the molecular weight of the obtained styrene resin increases, and a lower Dk and a lower Df can be achieved. [ka] (In formula (P), each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. y is an integer of 0 to 4.)

[0060] In formula (P), each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring, and has the same meaning as Arm in formula (T-OH), and the preferred range is also the same. When Arm is a benzene ring and y is an integer of 1 to 4, it is preferable that the OH group bonded to Arm and Mb are bonded at one or two of the ortho and para positions (preferably at least one or two of the ortho positions). In formula (P), Mb each independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom, and has the same meaning as Mb in formula (T-OH), and the preferred range is also the same. In formula (P), y represents an integer of 0 to 4 and has the same meaning as y in formula (T-OH), and the preferred range is also the same.

[0061] The compound represented by formula (P) preferably includes a compound represented by formula (P1). [ka] (In formula (P1), each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom; and y represents an integer of 0 to 4.) Mb and y in formula (P1) have the same meanings as Mb and y in formula (P), respectively, and the preferred ranges are also the same. In formula (P1), when y is an integer of 1 to 4, it is preferable that the OH group bonded to the benzene ring and Mb are bonded at one or two of the ortho and para positions (preferably at least one or two of the ortho positions).

[0062] Specific examples of the compound represented by formula (P) include cresols such as o-cresol, m-cresol, and p-cresol; phenol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol (2,6-dimethylphenol), 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; butylphenols such as isopropylphenol, butylphenol, and pt-butylphenol; p-pentylphenol, p-octylphenol, and p-nonylphenol. and p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; mono-substituted phenols such as o-phenylphenol, p-phenylphenol, 2-cyclohexylphenol, and 2-benzylphenol; condensed polycyclic phenols such as 1-naphthol, 2-naphthol, 1-anthracenol, and 2-anthracenol; polyhydric phenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, and phloroglucin. These phenols or derivatives thereof may be used alone or in combination of two or more. Among them, it is more preferable to use, as the compound represented by formula (P), a compound in which two of the ortho-positions and the para-positions relative to the phenolic hydroxyl group are alkyl-substituted (preferably a straight-chain alkyl-substituted compound, more preferably a compound substituted with a methyl group), such as 2,6-xylenol, 2,4-xylenol, or 2-cyclohexyl-6-methylphenol (preferably 2,6-xylenol or 2,4-xylenol). Furthermore, the compound represented by formula (P) is also preferably a compound having a group having a cyclic structure at the ortho-position of the phenolic hydroxyl group, such as 2-cyclohexylphenol and 2-benzylphenol. More specifically, the compound represented by formula (P) is preferably phenol, 2,6-xylenol, 2,4-xylenol, 2-cyclohexylphenol, 2-cyclohexyl-6-methylphenol, or 2-benzylphenol, and more preferably phenol, 2,6-xylenol, or 2-benzylphenol.

[0063] In this embodiment, when the compound represented by formula (P) is reacted with resin (T), the total content of m-bis(α-hydroxyisopropyl)benzene, p-bis(α-hydroxyisopropyl)benzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene in the reaction system is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the amount of resin (T). By making it equal to or less than the upper limit, the molecular weight of the hydroxy resin tends to be improved, which is preferable.

[0064] In addition, the molecular weight (Mw, Mn) of the hydroxy resin of this embodiment can be controlled by synthesizing it via the resin (T), the reaction temperature, the type and amount of catalyst, the reaction solvent, and the like.

[0065] In this embodiment, when the compound represented by formula (P) is reacted with the resin (T), the amount of the compound represented by formula (P) used is preferably 1 to 200 parts by mass per 100 parts by mass of the resin (T).

[0066] In this embodiment, the reaction temperature when the resin (T) is reacted with the compound represented by formula (P) is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, even more preferably 80°C or higher, even more preferably 100°C or higher, and even more preferably 120°C or higher. By setting the temperature at or above the lower limit, the reaction rate and the ratio of the indane skeleton (structural unit (a) in formula (Tx-OH)) tend to be improved, which is preferable. In addition, the reaction temperature is preferably 200°C or lower, more preferably 150°C or lower. By setting the temperature at or below the upper limit, the generation of by-products tends to be effectively suppressed. The reaction temperature does not need to be the same from the start to the end of the reaction, and may be changed. In this case, it is preferable that the average reaction temperature in the entire process is within the above range.

[0067] In the present embodiment, the catalyst used when reacting the resin (T) with the compound represented by formula (P) is not particularly limited, but may be an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, Lewis acids such as BF3 ether complex, BF3 phenol complex, aluminum chloride, zinc chloride, and indium chloride, solid acids such as activated clay, acid clay, silica alumina, and zeolite, heteropolyhydrochloric acid, and strong acid ion exchange resins. When a catalyst is used, the amount thereof is, for example, 0.01 to 30.0 parts by mass relative to 100 parts by mass of the raw material resin (T). The catalyst is usually one type alone, but two or more types may be used in combination. When using a combination of catalysts, it is preferable that the total amount is within the above range.

[0068] In this embodiment, the reaction solvent when reacting the resin (T) with the compound represented by formula (P) is not particularly specified, but may be used in combination with aromatic hydrocarbon solvents such as toluene, benzene, chlorobenzene, xylene, halogenated hydrocarbon solvents such as methylene chloride, chloroform, aliphatic hydrocarbon solvents such as hexane, heptane, ester solvents such as ethyl acetate, propyl acetate, amide solvents such as dimethylformamide, dimethylacetamide, alcohol solvents, or ketone solvents. Examples of alcohol solvents include methanol, ethanol, butanol, propanol, methyl propylene diglycol, diethylene glycol ethyl ether, butyl propylene glycol, propyl propylene glycol, etc. Examples of ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, methyl isobutyl ketone, etc., and others include tetrahydrofuran, dioxane, etc., but are not limited thereto. An example of the reaction solvent in this embodiment includes an aromatic hydrocarbon solvent.

[0069] In this embodiment, by using a solvent with high polarity, the intermediate carbocation can be stabilized, and a hydroxyl resin with a higher molecular weight can be obtained. When a solvent is used, the amount thereof is, for example, 10 to 1000 parts by mass per 100 parts by mass of the raw material resin (T). The solvent may be used alone or in combination of two or more. When two or more types are used, the mixture preferably has a content within the above range.

[0070] <Method of manufacturing styrene resin> The styrene resin of this embodiment can be produced by using the hydroxy resin of this embodiment. More specifically, the method for producing the styrene resin of this embodiment preferably includes reacting the hydroxy resin of this embodiment with a compound represented by formula (S). [ka] (In formula (S), Hr represents a chlorine atom or a bromine atom. Mc represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6. R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.

[0071] In formula (S), Hr represents a chlorine atom or a bromine atom, and a chlorine atom is preferred. In formula (S), Mc has the same meaning as Mc in formula (T-St), and the preferred range is also the same. In formula (S), z represents an integer of 0 to 4 and has the same meaning as z in formula (T-St), and the preferred range is also the same. In formula (S), r represents an integer of 1 to 6 and has the same meaning as r in formula (T-St), and the preferred range is also the same. In formula (S), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group; R in formula (T-St) 1 , R 2 , and R 3 and the preferred ranges are also the same.

[0072] When the hydroxy resin of the present embodiment is reacted with the compound represented by formula (S), the amount of the compound represented by formula (S) used is preferably 1 to 100 parts by mass per 100 parts by mass of the hydroxy resin.

[0073] The reaction temperature when reacting the hydroxy resin of this embodiment with the compound represented by formula (S) is preferably 50°C or higher and 100°C or lower.

[0074] When reacting the hydroxy resin of the present embodiment with the compound represented by formula (S), it is preferable to carry out the reaction in the presence of a solvent. As the solvent, aromatic hydrocarbon solvents such as toluene, benzene, chlorobenzene, xylene, etc., halogenated hydrocarbon solvents such as methylene chloride, chloroform, etc., aliphatic hydrocarbon solvents such as hexane, heptane, etc., ester solvents such as ethyl acetate, propyl acetate, etc., amide solvents such as dimethylformamide, dimethylacetamide, etc., alcohol solvents, or ketone solvents can be used in combination. As the alcohol solvent, methanol, ethanol, butanol, propanol, methyl propylene diglycol, diethylene glycol ethyl ether, butyl propylene glycol, propyl propylene glycol, etc. can be mentioned, and as the ketone solvent, acetone, methyl ethyl ketone, diethyl ketone, methyl butyl ketone, methyl isobutyl ketone, etc. can be mentioned, and others include tetrahydrofuran, dioxane, etc., but are not limited thereto. The solvent is, for example, used in an amount of about 100 to 1000 parts by mass per 100 parts by mass of the raw material hydroxy resin.

[0075] In the method for producing the styrene resin of this embodiment, it is preferable to synthesize the hydroxyl resin of this embodiment and a compound represented by formula (S) by subjecting them to a dehydrohalogenation reaction under basic conditions in the presence of a phase transfer catalyst. Representative examples of the phase transfer catalyst include tertiary amines such as triethylamine and tetramethylethylenediamine, quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltri-n-butylammonium chloride, benzyltri-n-butylammonium bromide, and benzyl-n-butylammonium iodide, and quaternary phosphonium salts, but are not limited thereto. In this embodiment, an example of the phase transfer catalyst is a quaternary ammonium salt. The phase transfer catalyst is, for example, used in an amount of about 1 to 100 parts by mass per 100 parts by mass of the raw material hydroxy resin.

[0076] The base may be an alkali metal-containing compound and / or an alkaline earth metal salt-containing compound. More specifically, representative examples of the base include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate. Needless to say, other bases may also be used. The base is, for example, used in an amount of about 1 to 100 parts by mass per 100 parts by mass of the raw material hydroxy resin.

[0077] In the method for producing a styrene resin according to the present embodiment, it is preferable to include a step of removing at least the compound represented by formula (S), preferably a low molecular weight compound (compound having a molecular weight of 400 or less) containing a chlorine atom and / or a bromine atom. By removing such a compound, the heat resistance of the resulting styrene resin is improved. In addition, the cured product of the resulting styrene resin tends to have a lower Dk and a lower Df. It is more preferable that the step of removing the compound represented by formula (S) is carried out after washing after the reaction of the hydroxy resin with the compound represented by formula (S).

[0078] <Resin composition> The resin composition of the present embodiment contains the styrene resin of the present embodiment. By containing the styrene resin of the present embodiment, the obtained cured product has excellent heat resistance and low dielectric properties (Dk and / or Df). The content of the styrene resin in the resin composition of this embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and may be 10 parts by mass or more, further may be 15 parts by mass or more, or may be 20 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the styrene resin in the resin composition of this embodiment may be 100 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, but is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less. The resin composition of the present embodiment may contain only one type of the styrene resin of the present embodiment, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0079] <Other resin components> The resin composition of the present embodiment may contain, in addition to the styrene resin of the present embodiment, a thermoplastic resin and / or other resin components other than the styrene resin of the present embodiment. In particular, the resin composition of the present embodiment preferably contains another curable compound (C) (preferably a thermosetting compound). The thermoplastic resin preferably contains an elastomer or a petroleum resin.

[0080] As the other curable compound (C), it is preferable to include at least one selected from the group consisting of polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the end, polymers having a structural unit represented by formula (V), maleimide compounds, cyanate ester compounds, epoxy compounds, phenol compounds, compounds containing a (meth)allyl group, oxetane resins, benzoxazine compounds, arylcyclobutene resins, polyamide resins, polyimide resins, perfluorovinyl ether resins, polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the end and compounds having a styrene group other than the styrene resin represented by formula (T-St), compounds having an isopropenyl group other than the resin represented by formula (T), and polyfunctional (meth)acrylate compounds other than the polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the end, and it is more preferable to include at least one selected from the group consisting of polyphenylene ether compounds having a carbon-carbon unsaturated double bond at the end, polymers having a structural unit represented by formula (V), and maleimide compounds. By including such components, the desired performance required for the printed wiring board can be more effectively exhibited. [ka] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0081] When the resin composition of the present embodiment contains other curable compounds (C), the content (total amount) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and may be 20 parts by mass or more, or 30 parts by mass or more, relative to 100 parts by mass of the resin solid content. By making it equal to or more than the lower limit, heat resistance, plating adhesion, low thermal expansion, etc. tend to be further improved. In addition, the upper limit of the content of the other curable compounds (C) is preferably 99 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 85 parts by mass or less, and may be 80 parts by mass or less, or 70 parts by mass or less, relative to 100 parts by mass of the resin solid content. By making it equal to or less than the upper limit, the low dielectric properties (Dk and / or Df) and low water absorption of the obtained cured product tend to be further improved. The resin composition of the present embodiment may contain only one type of other curable compound (C), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0082] <<Polyphenylene ether compound having terminal carbon-carbon unsaturated double bonds>> The resin composition of the present embodiment includes a polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond. In the present embodiment, the polyphenylene ether compound preferably includes a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds. The polyphenylene ether compound having a carbon-carbon unsaturated double bond at its terminal is preferably a polyphenylene ether compound having a group selected from the group consisting of a group represented by formula (Rx-1), such as a vinylbenzyl group, a group represented by formula (Rx-2), such as a (meth)acrylic group, and a maleimide group, at its terminal, more preferably a polyphenylene ether compound having a group represented by formula (Rx-1), such as a vinylbenzyl group, and / or a group represented by formula (Rx-2), such as a (meth)acrylic group, and even more preferably a polyphenylene ether compound containing two or more groups represented by formula (Rx-1), such as a vinylbenzyl group, and / or groups represented by formula (Rx-2), such as a (meth)acrylic group, at its terminal. [ka] (In formula (Rx-1) and formula (Rx-2), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. * is a bonding site with an oxygen atom. each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6.

[0083] By using these polyphenylene ether compounds, the low dielectric properties (Dk and / or Df) and low water absorption of printed wiring boards and the like tend to be more effectively improved. In this embodiment, polyphenylene ether compounds having vinylbenzyl groups at the terminals are particularly preferred. By having vinylbenzyl groups, the compatibility with the resin (A) tends to be significantly improved. These will be explained in detail below.

[0084] An example of a polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond (preferably a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds) is a compound having a phenylene ether skeleton represented by the following formula (X1).

[0085] [ka] (In formula (X1), R 24 , R 25 , R 26 , and R 27 may be the same or different and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.

[0086] The polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond (preferably a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds) is represented by the formula (X2): [ka] (In formula (X2), R 28 , R 29 , R 30 , R 34 , and R 35 R may be the same or different and represents an alkyl group having 6 or less carbon atoms or a phenyl group. 31 , R 32 , and R 33 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. and / or a repeating unit represented by the formula (X3): [ka] (In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , and R 43 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a straight-chain, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0087] The polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end (preferably, a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds) is preferably a modified polyphenylene ether compound in which a part or all of the end is functionalized with an ethylenically unsaturated group (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)"), and more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of a group represented by formula (Rx-1) such as a vinylbenzyl group, a group represented by formula (Rx-2) such as a (meth)acrylic group, and a maleimide group at the end, and further preferably a group represented by formula (Rx-1) such as a vinylbenzyl group and / or a group represented by formula (Rx-2) such as a (meth)acrylic group. By adopting such a modified polyphenylene ether compound (g), it is possible to further reduce the low dielectric properties (Dk and / or Df) of the cured product of the resin composition, and to increase the low water absorption and metal foil peel strength. These may be used alone or in combination of two or more.

[0088] The modified polyphenylene ether compound (g) may be a polyphenylene ether compound represented by the formula (OP). [ka] (In formula (OP), X represents an aromatic group, -(YO) n1 - represents a polyphenylene ether structure, n1 represents an integer of 1 to 100, and n2 represents an integer of 1 to 4. Rx is a group represented by formula (Rx-1) or formula (Rx-2). [ka] (In formula (Rx-1) and formula (Rx-2), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. * is a bonding site with an oxygen atom. each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6.

[0089] When n1 and / or n2 are integers of 2 or more, the n1 structural units (YO) and / or the n2 structural units may be the same or different. n2 is preferably 2 or more, and more preferably 2.

[0090] In formula (Rx-1) and formula (Rx-2), R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. R 1 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom. R 2 and R 3 are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom. R 1 , R 2 , and R 3 The number of carbon atoms in the alkyl group, alkenyl group, or alkynyl group is preferably 5 or less, and more preferably 3 or less.

[0091] In formula (Rx-1), r represents an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and even more preferably 1.

[0092] In formula (Rx-1), each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, further preferably a methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, octyl group, or nonyl group, and still more preferably a methyl group, ethyl group, isopropyl group, isobutyl group, or t-butyl group. In formula (Rx-1), z represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and even more preferably 0.

[0093] A specific example of the group represented by formula (Rx-1) is a vinylbenzyl group, and a specific example of the group represented by formula (Rx-2) is a (meth)acryloyl group. Rx is preferably a group represented by formula (Rx-1).

[0094] The modified polyphenylene ether compound (g) may be a polyphenylene ether compound represented by the formula (OP-1). [ka] In formula (OP-1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 , and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4. When n2 and / or n3 are integers of 2 or more, the n2 constitutional units (YO) and / or the n3 constitutional units may be the same or different. n3 is preferably 2 or more, and more preferably 2.

[0095] The modified polyphenylene ether compound (g) in this embodiment is preferably a compound represented by formula (OP-2), and more preferably a compound represented by formula (OP-2-2). [ka] [ka] Here, -(OXO)- is represented by the formula (OP-3): [ka] (In formula (OP-3), R 4 , R 5 , R 6 , R 10 , and R 11 R may be the same or different and is an alkyl group or a phenyl group having 6 or less carbon atoms. 7 , R 8 , and R 9 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. and / or formula (OP-4): [ka] (In formula (OP-4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0096] Also, -(YO)- is a group represented by the formula (OP-5): [ka] (In formula (OP-5), R 20 , R 21 R may be the same or different and is an alkyl group or a phenyl group having 6 or less carbon atoms. 22 , R 23 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. 20 and R 21By each independently having one or more methyl groups and / or cyclohexyl groups, the rigidity of the resulting resin molecules increases. Since molecules with high rigidity have lower mobility compared to molecules with low rigidity, the relaxation time during dielectric relaxation becomes longer, which is preferable for improving low dielectric properties (Dk and / or Df). An example of formula (OP-5) has the following structure. [Chemical formula] Regarding the polyphenylene compound having the above structure, the description in JP-A-2019-194312 can be referred to, and this content is incorporated herein.

[0097] In formula (OP-2), a and b each independently represent an integer from 0 to 100, and at least one of a and b is an integer from 1 to 100. Preferably, a and b are each independently an integer from 0 to 50, more preferably an integer from 1 to 30, and still more preferably an integer from 1 to 10. When a and / or b is an integer of 2 or more, two or more -(Y-O)- may each independently have one kind of structure arranged, or two or more kinds of structures may be arranged in blocks or randomly. Further, when containing a plurality of compounds represented by formula (OP-2), the average value of a is preferably 1 < a < 10, and the average value of b is preferably 1 < b < 10.

[0098] Examples of -A- in formula (OP-4) include divalent organic groups such as a methylene group, an ethylidene group, a 1-methylethylidene group, a 1,1-propylidene group, a 1,4-phenylenebis(1-methylethylidene) group, a 1,3-phenylenebis(1-methylethylidene) group, a cyclohexylidene group, a phenylmethylene group, a naphthylmethylene group, and a 1-phenylethylidene group, but are not limited thereto.

[0099] Rx has the same meaning as Rx in formula (OP), and the preferred range is also the same.

[0100] Among the compounds represented by the above formula (OP-2), R 4 , R 5 , R 6 , R 10 , R 11 , R 20 , and R 21 is an alkyl group having 3 or less carbon atoms, and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 , and R 23 is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and it is particularly preferred that -(OXO)- represented by formula (OP-3) or formula (OP-4) is formula (OP-9), formula (OP-10), and / or formula (OP-11), and -(YO)- represented by formula (OP-5) is formula (OP-12) or formula (OP-13). When a and / or b are integers of 2 or more, the two or more -(YO)- may each independently be a structure in which two or more of formula (OP-12) and / or formula (OP-13) are arranged, or a structure in which formula (OP-12) and formula (OP-13) are arranged in blocks or randomly.

[0101] [ka] [ka] (In formula (OP-10), R 44 , R 45 , R 46 , and R 47 may be the same or different and are a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Specific examples of -B- include the same as the specific examples of -A- in formula (OP-4). [ka] (In formula (OP-11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.) Specific examples of -B- include the same as the specific examples of -A- in formula (OP-4). [ka] [ka]

[0102] The modified polyphenylene ether compound (g) used in this embodiment is more preferably a compound represented by formula (OP-14) and / or a compound represented by formula (OP-15). [ka] (In formula (OP-14), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.) In formula (OP-14), a and b each independently have the same definition as a and b in formula (OP-2), and the preferred ranges are also the same. [ka] (In formula (OP-15), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.) In formula (OP-15), a and b each independently have the same definition as a and b in formula (OP-2), and the preferred ranges are also the same.

[0103] The polystyrene-equivalent number average molecular weight (Mn) of the polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond (preferably a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, more preferably a modified polyphenylene ether compound (g)) measured by GPC (gel permeation chromatography) method (details are in accordance with the method described in the Examples below) is, for example, preferably 500 or more, further preferably 800 or more, and also preferably 3,000 or less. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film. When the number average molecular weight is 3,000 or less, solubility in a solvent tends to be further improved. Furthermore, the polystyrene-equivalent weight average molecular weight (Mw) of the polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond (preferably a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, more preferably a modified polyphenylene ether compound (g)) measured by GPC (details are according to the method described in the Examples below) is preferably 800 to 6000, more preferably 800 to 5000. By making it equal to or more than the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and by making it equal to or less than the upper limit, the solubility, low viscosity and moldability of the resin composition in a solvent when preparing a varnish or the like described below tend to be further improved. Furthermore, in the case of the modified polyphenylene ether compound (g), the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, more preferably 400 to 2500 g. By making it equal to or greater than the lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower. By making it equal to or less than the upper limit, the solubility in the solvent, low viscosity, and moldability of the resin composition tend to be improved.

[0104] The lower limit of the content of the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end in the resin composition of this embodiment (preferably, a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds) is 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, even more preferably 150 parts by mass or more, and may be 180 parts by mass or more, relative to 100 parts by mass of the resin (A). By making it equal to or more than the lower limit, the moldability of the resin composition, the low water absorption of the obtained cured product, and the low dielectric properties (Dk and / or Df) tend to be further improved. In addition, the upper limit of the content of the polyphenylene ether compound having a carbon-carbon unsaturated double bond at the end (preferably, a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds) is 300 parts by mass or less, preferably 280 parts by mass or less, more preferably 250 parts by mass or less, and even 220 parts by mass or less, relative to 100 parts by mass of the resin (A). By ensuring that the content is equal to or less than the above upper limit, the low dielectric properties (Dk and / or Df), heat resistance and chemical resistance of the resulting cured product tend to be improved.

[0105] The total content of the resin (A) and the polyphenylene ether compound relative to 100 parts by mass of the resin solid content in the resin composition of this embodiment is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, even more preferably 50 parts by mass or more, and may be 55 parts by mass or more. By making the total content of the resin (A) and the polyphenylene ether compound equal to or more than the lower limit, the low water absorption and low dielectric properties (Dk and / or Df) of the obtained cured product tend to be further improved. In addition, the total content of the resin (A) and the polyphenylene ether compound relative to 100 parts by mass of the resin solid content in the resin composition is preferably 80 parts by mass or less. By making the total content of the resin (A) and the polyphenylene ether compound equal to or less than the upper limit, the moldability of the resin composition, the low dielectric properties (Dk and / or Df), heat resistance, chemical resistance, and the like of the obtained cured product tend to be excellent in balance. The resin composition in the present embodiment may contain only one type of polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0106] <<Polymer having a structural unit represented by formula (V)>> The resin composition of the present embodiment preferably contains a polymer having a constitutional unit represented by formula (V). By containing a polymer having a constitutional unit represented by formula (V), a resin composition capable of providing a cured product having excellent low dielectric properties (Dk and / or Df) can be obtained. [ka] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0107] The aromatic hydrocarbon linking group may be a group consisting of only aromatic hydrocarbons which may have a substituent, or may be a group consisting of a combination of aromatic hydrocarbons which may have a substituent and other linking groups, and is preferably a group consisting of only aromatic hydrocarbons which may have a substituent. The substituent that the aromatic hydrocarbon may have includes a substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, an amino group, a carboxy group, a halogen atom, etc.). It is also preferable that the aromatic hydrocarbon does not have a substituent. The aromatic hydrocarbon linking group is usually a divalent linking group.

[0108] Specific examples of the aromatic hydrocarbon linking group include phenylene, naphthalenediyl, anthracenediyl, phenanthrenediyl, biphenyldiyl, and fluorenediyl groups, which may have a substituent, and among these, phenylene groups which may have a substituent are preferred. Examples of the substituent include the above-mentioned substituent Z, but it is preferred that the above-mentioned phenylene groups and other groups do not have a substituent.

[0109] The constitutional unit represented by formula (V) more preferably includes at least one of a constitutional unit represented by the following formula (V1), a constitutional unit represented by the following formula (V2), and a constitutional unit represented by the following formula (V3). In the following formula, * represents a bonding position. In addition, hereinafter, the constitutional units represented by formulas (V1) to (V3) may be collectively referred to as "constituent unit (a)".

[0110] [ka] In formulas (V1) to (V3), L 1 is an aromatic hydrocarbon linking group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms). Specific examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a fluorenediyl group, each of which may have a substituent, and among these, a phenylene group which may have a substituent is preferred. Examples of the substituent include the above-mentioned substituent Z, but it is preferable that the above-mentioned phenylene group and other groups do not have a substituent. The compound forming the structural unit (a) is preferably a divinyl aromatic compound, such as divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, and divinylphenanthrene. Among them, divinylbenzene is particularly preferred. These divinyl aromatic compounds may be used alone or in combination as necessary.

[0111] As described above, the polymer having the structural unit represented by formula (V) may be a homopolymer of the structural unit (a), but it may also be a copolymer with a structural unit derived from another monomer. When the polymer having the structural unit represented by formula (V) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and may be 15 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly more preferably 30 mol% or less, and may even be 25 mol% or less, 20 mol% or less.

[0112] An example of a structural unit derived from another monomer is the structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound).

[0113] The structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).

[0114] [ka] In formula (V4), L 2 is an aromatic hydrocarbon linking group, and preferred examples thereof include the above L 1 Examples include: R V1 R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). V1 When R is a hydrocarbon group, it preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. V1 and L 2 may have the above-mentioned substituent Z.

[0115] When the polymer having the structural unit represented by formula (V) is a copolymer containing the structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include vinyl aromatic compounds such as styrene, vinylnaphthalene, and vinylbiphenyl; and nucleus alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compounds exemplified here may have the above-mentioned substituent Z as appropriate. In addition, these monovinyl aromatic compounds may be used alone or in combination.

[0116] When the polymer having the structural unit represented by formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more, and may be 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 75 mol% or more. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.

[0117] The polymer having the structural unit represented by formula (V) may have other structural units other than the structural unit (a) and the structural unit (b). Examples of the other structural units include structural units (c) derived from cycloolefin compounds. Examples of cycloolefin compounds include hydrocarbons having a double bond in the ring structure. Specifically, in addition to monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds in which aromatic rings such as indene and acenaphthylene are condensed can be mentioned. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of JP 2018-39995 A, the contents of which are incorporated herein. The cycloolefin compounds exemplified here may further have the above-mentioned substituent Z.

[0118] When the polymer having the structural unit represented by formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, and may be 50 mol% or less, or may be 30 mol% or less.

[0119] A polymer having a structural unit represented by formula (V) may further incorporate a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compound). Examples of other polymerizable compounds (monomers) include compounds containing three vinyl groups. Specific examples include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Alternatively, examples include ethylene glycol diacrylate and butadiene. The copolymerization ratio of the structural unit (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.

[0120] An example of a polymer having a structural unit represented by formula (V) is a polymer that essentially contains the structural unit (a) and at least one of the structural units (b) to (d). Further, an example is one in which the total of the structural units (a) to (d) accounts for 95 mol % or more, and further 98 mol % or more of all the structural units. In another embodiment of the polymer having a structural unit represented by formula (V), the structural unit (a) is essential, and of all structural units excluding the terminals, structural units containing an aromatic ring preferably account for 90 mol % or more, more preferably 95 mol % or more, and may even account for 100 mol %. In calculating the mole percentage per total structural units, one structural unit is defined as being derived from one molecule of a monomer (e.g., a divinyl aromatic compound, a monovinyl aromatic compound, etc.) used in the production of a polymer having a structural unit represented by formula (V).

[0121] The method for producing the polymer having the structural unit represented by formula (V) is not particularly limited and may be a conventional method, for example, a raw material containing a divinyl aromatic compound (if necessary, in the presence of a monovinyl aromatic compound, a cycloolefin compound, etc.) is polymerized in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, a metal fluoride such as boron trifluoride or a complex thereof can be used.

[0122] The structure of the chain end of the polymer having the structural unit represented by formula (V) is not particularly limited, but in terms of the group derived from the above-mentioned divinyl aromatic compound, it may have the structure of the following formula (E1). 1 is the same as defined in formula (V1) above. * represents a bond position. *-CH=CH-L 1 -CH=CH2(E1)

[0123] When a group derived from a monovinyl aromatic compound is at the chain end, the structure may be that of the following formula (E2): 2 and R V1are the same as defined in formula (V4) above. * represents a bond position. *-CH=CH-L 2 -R V1 (E2)

[0124] The molecular weight of the polymer having a constitutional unit represented by formula (V) is preferably 300 or more, more preferably 500 or more, even more preferably 1,000 or more, and even more preferably 1,500 or more, in terms of number average molecular weight Mn. The upper limit is preferably 130,000 or less, more preferably 120,000 or less, even more preferably 110,000 or less, and even more preferably 100,000 or less. The molecular weight of the polymer having the structural unit represented by formula (V) is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, in terms of weight average molecular weight Mw. By making it equal to or greater than the lower limit, the excellent low dielectric properties of the polymer having the structural unit represented by formula (V), particularly Df and dielectric properties after moisture absorption, can be effectively exhibited in the cured product of the resin composition. The upper limit is preferably 130,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 50,000 or less. By making it equal to or less than the upper limit, embedding defects tend to be less likely to occur when the prepreg or resin sheet is laminated on a circuit board. The monodispersity (Mw / Mn), which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less. As the lower limit, a practical value is 1.1 or more, preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more. The above Mw and Mn are measured according to the description in the Examples section below. When the resin composition of the present embodiment contains two or more polymers having a structural unit represented by formula (V), it is preferable that the Mw, Mn and Mw / Mn of the mixture satisfy the above ranges.

[0125] The vinyl group equivalent of the polymer having the structural unit represented by formula (V) is preferably 200 g / eq. or more, more preferably 230 g / eq. or more, and even more preferably 250 g / eq. or more. The vinyl group equivalent is preferably 1200 g / eq. or less, more preferably 1000 g / eq. or less, and may be 800 g / eq. or less, 600 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less. By making it equal to or greater than the lower limit, the storage stability of the resin composition tends to be improved and the flowability of the resin composition tends to be improved. Therefore, moldability is improved, voids are less likely to occur during the formation of prepregs, etc., and a more reliable printed wiring board tends to be obtained. On the other hand, by making it equal to or less than the upper limit, the heat resistance of the obtained cured product tends to be improved.

[0126] For the polymer having a constitutional unit represented by formula (V) in this specification, the compounds described in paragraphs 0029 to 0058 of International Publication No. 2017 / 115813 and their synthesis reaction conditions, etc., the compounds described in paragraphs 0013 to 0058 of JP-A-2018-039995 and their synthesis reaction conditions, etc., the compounds described in paragraphs 0008 to 0043 of JP-A-2018-168347 and their synthesis reaction conditions, etc., the compounds described in paragraphs 0014 to 0042 of JP-A-2006-070136 and their synthesis reaction conditions, etc., the compounds described in paragraphs 0014 to 0061 of JP-A-2006-089683 and their synthesis reaction conditions, etc., the compounds described in paragraphs 0008 to 0036 of JP-A-2008-248001 and their synthesis reaction conditions, etc. can be referenced, and are incorporated herein.

[0127] The lower limit of the content of the polymer having the structural unit represented by formula (V) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, when the resin solid content in the resin composition is 100 parts by mass. On the other hand, the upper limit of the content of the polymer having the structural unit represented by formula (V) is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less, when the resin solid content in the resin composition is 100 parts by mass.

[0128] <<Maleimide compounds>> The resin composition of the present embodiment may contain a maleimide compound. The maleimide compound is not particularly limited as long as it contains one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably) maleimide groups in the molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used. In the present embodiment, the maleimide compound preferably includes one or more selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M2), a compound represented by formula (M3), a compound represented by formula (M4), a compound represented by formula (M5), a maleimide compound (M6), and a maleimide compound (M7), and the maleimide compound selected from the group consisting of a compound represented by formula (M0), a compound represented by formula (M1), a compound represented by formula (M3), a compound represented by formula (M4), a compound represented by formula (M5), and a maleimide compound (M6). It is more preferable to include one or more selected from the group consisting of a compound represented by formula (M1), a compound represented by formula (M3), a compound represented by formula (M4), and a compound represented by formula (M5), it is even more preferable to include one or more selected from the group consisting of a compound represented by formula (M1), a compound represented by formula (M3), and a compound represented by formula (M5), it is even more preferable to include a compound represented by formula (M1) and / or a compound represented by formula (M3), and it is even more preferable to include a compound represented by formula (M1). When these maleimide compounds are used in materials for printed wiring boards (e.g., metal foil-clad laminates), etc., excellent heat resistance can be imparted.

[0129] [ka] (In formula (M0), R 51 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; R 52 each independently represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 or more. R 51 are each independently preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a phenyl group, more preferably a hydrogen atom and / or a methyl group, and even more preferably a hydrogen atom. R 52 is preferably a methyl group. n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and even more preferably 1. Specifically, the following compounds are preferred examples of the formula (M0). [ka] In the above formula, R 8 each independently represents a hydrogen atom, a methyl group or an ethyl group, and is preferably a methyl group.

[0130] The compound represented by formula (M0) may be a single type or a mixture of two or more types. Examples of the mixture include a mixture of compounds with different n1, 51 and / or R 52 Examples of the compound include a mixture of compounds having different types of substituents, a mixture of compounds having different bonding positions (meta, para, ortho positions) of the maleimide group and the oxygen atom on the benzene ring, and a mixture of compounds having a combination of two or more of the above differences. The same applies to the compounds represented by the formulae (M1) to (M6) below. [ka] (In formula (M1), R M1 , R M2 , R M3 , and R M4 R each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R M7 and R M8 are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R M9 and R M10 R each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 , and R M14R each independently represents a hydrogen atom or an organic group. M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20.)

[0131] R in the formula M1 , R M2 , R M3 , and R M4 R each independently represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M1 and R M3 are each independently preferably an alkyl group, and R M2 and R M4 is preferably a hydrogen atom. R M5 and R M6 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. Ar M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, or an anthracenediyl group, more preferably a phenylene group, and further preferably an m-phenylene group. M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. Mis preferably unsubstituted. A is a 4- to 6-membered alicyclic group, and more preferably a 5-membered alicyclic group (preferably a group which forms an indan ring when combined with a benzene ring). M7 and R M8 are each independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. mx is 1 or 2, and is preferably 2. lx is 0 or 1, and is preferably 1. R M9 and R M10 are each independently a hydrogen atom or an alkyl group, more preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M11 , R M12 , R M13 , and R M14 R each independently represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 is preferably a hydrogen atom. R M15 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, and is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. nx represents an integer of 1 to 20. nx may be an integer of 10 or less. The resin composition of the present embodiment may contain only one type of compound represented by formula (M1) having at least different values ​​of nx, or may contain two or more types. When two or more types are contained, the average value (average number of repeating units) n of nx in the compound represented by formula (M1) in the resin composition is preferably 0.92 or more, more preferably 0.95 or more, even more preferably 1.0 or more, and even more preferably 1.1 or more, in order to obtain a low melting point (low softening point), low melt viscosity, and excellent handleability. In addition, n is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, even more preferably 6.0 or less, and may be 5.0 or less. The same applies to the compounds represented by formulas (M1-2) and (M1-3) described later. The compound represented by formula (M1) is preferably a compound represented by the following formula (M1-1). [ka] (In formula (M1-1), R M21 , R M22 , R M23 , and R M24 R each independently represents a hydrogen atom or an organic group. M25 and R M26 R each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 , and R M30 R each independently represents a hydrogen atom or an organic group. M31 and R M32 R each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , R M35 , and R M36 R each independently represents a hydrogen atom or an organic group. M37, R M38 , and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 or more and 20 or less.

[0132] R in the formula M21 , R M22 , R M23 , and R M24 R each independently represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M21 and R M23 is preferably an alkyl group, R M22 and R M24 is preferably a hydrogen atom. R M25 and R M26 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M27 , R M28 , R M29 , and R M30 each independently represents a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M31 and R M32 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M33 , RM34 , R M35 , and R M36 each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M33 and R M36 is preferably a hydrogen atom, R M34 and R M35 is preferably an alkyl group. R M37 , R M38 , and R M39 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. nx represents an integer of 1 or more and 20 or less. nx may be an integer of 10 or less.

[0133] The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-2). [ka] (In formula (M1-2), R M21 , R M22 , R M23 , and R M24 R each independently represents a hydrogen atom or an organic group. M25 and R M26 R each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 , and R M30 R each independently represents a hydrogen atom or an organic group. M31 and R M32 R each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , RM35 , and R M36 R each independently represents a hydrogen atom or an organic group. M37 , R M38 , and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 or more and 20 or less.

[0134] In formula (M1-2), R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx are R in formula (M1-1), M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx, and the preferred ranges are also the same.

[0135] The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-3), and more preferably a compound represented by the following formula (M1-4). [ka] (In formula (M1-3), nx represents an integer of 1 or more and 20 or less.) nx may be an integer less than or equal to 10. [ka] (In formula (M1-4), nx represents an integer of 1 or more and 20 or less.) nx may be an integer less than or equal to 10.

[0136] The molecular weight of the compound represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. By making it equal to or more than the lower limit, the low dielectric properties (Dk and / or Df) and low water absorption of the obtained cured product tend to be improved. In addition, the molecular weight of the compound represented by formula (M1) is preferably 10000 or less, more preferably 9000 or less, even more preferably 7000 or less, even more preferably 5000 or less, and even more preferably 4000 or less. By making it equal to or less than the upper limit, the heat resistance and handleability of the obtained cured product tend to be improved.

[0137] The compound represented by formula (M1) preferably has a maleimide group equivalent of 50 g / eq. or more, more preferably 100 g / eq. or more, and even more preferably 200 g / eq. or more. The upper limit of the maleimide equivalent is preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, and even more preferably 800 g / eq. or less. Here, the maleimide group equivalent represents the mass of the maleimide compound per equivalent of maleimide group. When the maleimide group equivalent of the compound represented by formula (M1) is within the above range, the obtained cured product tends to have improved low dielectric properties (Dk and / or Df), low water absorption, heat resistance, and handleability.

[0138] The compound represented by formula (M1) preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) measurement of 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and even more preferably 1.3 to 3.4. When the Mw / Mn of the compound represented by formula (M1) is within the above range, the low dielectric properties (Dk and / or Df), low water absorbency, heat resistance, and handleability of the obtained cured product tend to be further improved.

[0139] For other details of the compound represented by formula (M1), refer to the descriptions in International Publication No. 2020-217679, the contents of which are incorporated herein by reference.

[0140] [ka] (In formula (M2), R 54 each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or greater. n4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and may be 1. The compound represented by formula (M2) may be a mixture of compounds having different n4, and is preferably a mixture. As described for the compound represented by formula (M0), the compound may be a mixture of compounds having different other moieties. [ka] (In formula (M3), R 55 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 or more and 10 or less. R 55are each independently preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a phenyl group, more preferably a hydrogen atom and / or a methyl group, and even more preferably a hydrogen atom. n5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2. The compound represented by formula (M3) may be a mixture of compounds having different n5, and is preferably a mixture. As described for the compound represented by formula (M0), the compound may be a mixture of compounds having different other moieties. [ka] (In formula (M4), R 56 each independently represents a hydrogen atom, a methyl group, or an ethyl group; R 57 each independently represents a hydrogen atom or a methyl group. R 56 are preferably each independently a methyl group or an ethyl group, and more preferably a methyl group and an ethyl group in each of the two benzene rings; R 57 is preferably a methyl group.

[0141] [ka] (In formula (M5), R 58 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; R 59 each independently represents a hydrogen atom or a methyl group, and n6 represents an integer of 1 or more. R 58 are each independently preferably one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a phenyl group, more preferably a hydrogen atom and / or a methyl group, and even more preferably a hydrogen atom. R 59 is preferably a methyl group. n6 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, still more preferably 1 or 2, and may be 1. The compound represented by formula (M5) may be a mixture of compounds having different n6, and is preferably a mixture. As described for the compound represented by formula (M0), the compound may be a mixture of compounds having different other moieties.

[0142] The maleimide compound (M6) is a compound having a constitutional unit represented by the formula (M6) and maleimide groups at both ends of the molecular chain. [ka] (In formula (M6), R 61 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 62 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 63 each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. Each n independently represents an integer of 0 to 10. For details of the maleimide compound (M6) and its manufacturing method, please refer to paragraphs 0061 to 0066 of WO 2020 / 262577, the contents of which are incorporated herein by reference.

[0143] The maleimide compound (M7) is a maleimide compound obtained by reacting, as reaction raw materials (1), an aromatic amine compound (a1) having one to three alkyl groups on an aromatic ring, an aromatic divinyl compound (a2) having two ethenyl groups, and maleic anhydride. The maleimide compound (M7) is preferably a compound represented by the formula (M7). [ka] (In the above formula (M7), R 1 each independently represents the alkyl group; R 2 each independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or a methyl group, and R 3 and R 4 One of the groups is a hydrogen atom and the other is a methyl group, and R 5 and R 6 one of which is a hydrogen atom and the other is a methyl group, X 1 is the following formula (x): [ka] (In formula (x), R 7 and R 8 each independently represents a hydrogen atom or a methyl group, and R 7 and R 8 One of the groups is a hydrogen atom and the other is a methyl group, and R 9 each independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4. and r represents a substituent represented by X 1 X per benzene ring to which 1 is the average number of substitutions, and represents a number from 0 to 4, p represents an integer from 1 to 3, q ​​represents an integer from 0 to 4, and k represents an integer from 1 to 100.

[0144] For details of the polymaleimide compound (M7) used in this embodiment, refer to the description in Japanese Patent No. 7160151, the contents of which are incorporated herein by reference.

[0145] The maleimide compound may be produced by a known method, or a commercially available product may be used. Examples of commercially available products include "BMI-80" manufactured by K.I. Kasei Co., Ltd. as a compound represented by formula (M0), "NE-X-9470S" manufactured by DIC Corporation as a compound represented by formula (M1), "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (M2), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M3), "BMI-70" manufactured by K.I. Kasei Co., Ltd. as a compound represented by formula (M4), "MIR-5000" manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (M5), "MIZ-001" manufactured by Nippon Kayaku Co., Ltd. as a maleimide compound (M6), and "NE-X-9500" manufactured by DIC Corporation as a maleimide compound (M7).

[0146] Examples of maleimide compounds other than those mentioned above include N-phenylmaleimide, N-cyclohexylmaleimide, phenylmethanemaleimide oligomers, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers of these, and prepolymers of these maleimides and amines. In particular, when a monofunctional maleimide compound such as N-phenylmaleimide or N-cyclohexylmaleimide is used in combination with a polymer having a structural unit represented by the following formula (V), a resin composition capable of providing a cured product with excellent low dielectric properties tends to be obtained.

[0147] When the resin composition of the present embodiment contains a maleimide compound, the lower limit of the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the maleimide compound is 1 part by mass or more, the flame resistance of the obtained cured product tends to be improved. In addition, the upper limit of the content of the maleimide compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and may be 40 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the maleimide compound is 70 parts by mass or less, the metal foil peel strength and low water absorption of the obtained cured product tend to be improved. The resin composition in the present embodiment may contain only one type of maleimide compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition in this embodiment may be configured to be substantially free of a maleimide compound, which means that the content of the maleimide compound is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0148] <<Cyanate ester compounds>> The resin composition of the present embodiment may contain a cyanate ester compound. The cyanate ester compound is not particularly limited as long as it contains one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) cyanate groups (cyanato groups) in the molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0149] The cyanate ester compound is preferably a cyanate ester compound having two or more aromatic moieties substituted with at least one cyanato group in the molecule, which is commonly used in printed wiring boards. Specifically, the lower limit of the number of cyanate groups in the cyanate ester compound is preferably 2 or more, more preferably 3 or more. By making it equal to or more than the above lower limit, the heat resistance tends to be further improved. In addition, the upper limit of the number of cyanate groups is preferably 100 or less, more preferably 50 or less. In addition, the cyanate ester compound is preferably cured with excellent low dielectric properties (Dk and / or Df). For example, the cured cyanate ester compound has a dielectric constant (Dk) of 4.0 or less, more preferably 3.5 or less, at a frequency of 10 GHz, measured according to the cavity resonance perturbation method. The lower limit of the dielectric constant is, for example, 2.0 or more, which is practical. In addition, the cured cyanate ester compound (B) has a dielectric loss tangent (Df) of 0.02 or less, more preferably 0.015 or less, at a frequency of 10 GHz, measured according to the cavity resonance perturbation method. The lower limit of the dielectric loss tangent is, for example, 0.0001 or more, which is practical. The dielectric constant and dielectric loss tangent can be measured, for example, according to the method described in the examples (curing conditions, measurement conditions).

[0150] In addition, the cyanate ester compound preferably has high heat resistance in its cured product. The cured product of the cyanate ester compound preferably has a glass transition temperature of 150° C. or higher, more preferably 180° C. or higher, and even more preferably 200° C. or higher, as measured according to JIS C6481 dynamic viscoelasticity measurement. By setting the glass transition temperature to the lower limit or higher, a cured product with excellent heat resistance can be obtained.

[0151] The weight average molecular weight of the cyanate ester compound, calculated as polystyrene by the GPC method, is preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more. By making the weight average molecular weight equal to or greater than the lower limit, the heat resistance tends to be improved. In addition, the weight average molecular weight of the cyanate ester compound is preferably 1000 or less, more preferably 900 or less, and even more preferably 800 or less. By making the weight average molecular weight equal to or less than the upper limit, the moldability and handling properties tend to be improved.

[0152] For a preferred range of the cyanate ester compound, reference can be made to paragraphs 0028 to 0033 of WO 2021 / 172317, the contents of which are incorporated herein by reference.

[0153] A preferred cyanate ester compound is at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanates), naphthylene ether type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, xylene resin type cyanate ester compounds, trisphenolmethane type cyanate ester compounds, adamantane skeleton type cyanate ester compounds, bisphenol M type cyanate ester compounds, and bisphenol A type cyanate ester compounds. Among these, from the viewpoint of further improving low water absorbency, at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, bisphenol M type cyanate ester compounds, and bisphenol A type cyanate ester compounds is preferable, at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, bisphenol A type cyanate ester compounds, and bisphenol M type cyanate ester compounds is more preferable, at least one selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, and bisphenol A type cyanate ester compounds is even more preferable, naphthol aralkyl type cyanate ester compounds and / or bisphenol A type cyanate ester compounds are even more preferable, and naphthol aralkyl type cyanate ester compounds are even more preferable.

[0154] The naphthol aralkyl cyanate compound is more preferably a compound represented by the formula (N1).

[0155] Formula (N1) [ka] (In formula (N1), R 3 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or greater.

[0156] In formula (N1), R 3 each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred. In formula (N1), n3 is an integer of 1 or more, preferably an integer of 1 to 50, more preferably an integer of 1 to 20, even more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.

[0157] The phenol novolac type cyanate ester compound is not particularly limited, but is preferably, for example, a compound represented by formula (VII). [ka] (In formula (VII), R 6 each independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or greater.

[0158] In formula (VII), R 6 each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred. In formula (VII), n7 is an integer of 1 or more, and is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.

[0159] As the bisphenol A type cyanate ester compound, one or more compounds selected from the group consisting of 2,2-bis(4-cyanatophenyl)propane and prepolymers of 2,2-bis(4-cyanatophenyl)propane may be used.

[0160] These cyanate ester compounds may be prepared by known methods, or may be commercially available products. Note that cyanate ester compounds having naphthol aralkyl skeleton, naphthylene ether skeleton, xylene skeleton, trisphenolmethane skeleton, or adamantane skeleton have a relatively large functional group equivalent number and a small amount of unreacted cyanate ester groups, so that resin compositions using these tend to have even better low water absorption. In addition, mainly due to the presence of an aromatic skeleton or adamantane skeleton, plating adhesion tends to be even better.

[0161] When the resin composition of the present embodiment contains a cyanate ester compound, it is preferable to include it within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a cyanate ester compound, the lower limit of the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the cyanate ester compound is 1 part by mass or more, the heat resistance, flame resistance, chemical resistance, and insulating properties of the obtained cured product tend to be improved. When the resin composition of the present embodiment contains a cyanate ester compound, the upper limit of the content of the cyanate ester compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and may be 15 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. The resin composition in the present embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition in this embodiment may be configured to be substantially free of cyanate ester compounds. Substantially free means that the content of the cyanate ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0162] <<Epoxy compounds>> The resin composition of the present embodiment may contain an epoxy compound. The epoxy compound is not particularly limited as long as it is a compound or resin having one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) epoxy groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, compounds in which the double bond of butadiene is epoxidized, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, etc. By using these, the moldability and adhesion of the resin composition are improved. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferred, and biphenyl aralkyl type epoxy resins are more preferred.

[0163] The resin composition of the present embodiment preferably contains an epoxy compound in a range that does not impair the effects of the present invention. From the viewpoint of moldability and adhesion, when the resin composition of the present embodiment contains an epoxy compound, the content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the epoxy compound is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved. When the resin composition of the present embodiment contains an epoxy compound, the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, and may be 8 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the epoxy compound is 50 parts by mass or less, the electrical properties of the obtained cured product tend to be improved. The resin composition in the present embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition in the present embodiment may be configured to be substantially free of epoxy compounds. Substantially free means that the content of the epoxy compounds is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and may even be less than 0.001 parts by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0164] <<Phenol compounds>> The resin composition of the present embodiment may contain a phenol compound. For details of the phenolic resin, please refer to paragraph 0049 of International Publication No. 2021 / 172317, the contents of which are incorporated herein by reference.

[0165] The resin composition of the present embodiment preferably contains a phenolic compound in an amount not impairing the effects of the present invention. When the resin composition of the present embodiment contains a phenolic compound, the content of the phenolic compound is preferably 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition. The resin composition in the present embodiment may contain only one type of phenol compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may be configured to be substantially free of phenol compounds, which means that the content of phenol compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0166] <<Compounds containing (meth)allyl groups>> The resin composition of the present embodiment preferably contains a compound containing a (meth)allyl group, and more preferably contains a compound containing an allyl group. Moreover, the compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups. The compound containing a (meth)allyl group preferably contains at least one selected from the group consisting of a (meth)allyl isocyanurate compound, a tri(meth)allyl cyanurate compound, a (meth)allyl group-substituted nadimide compound, a (meth)allyl compound having a glycoluril structure, and a diallyl phthalate, more preferably contains at least one selected from the group consisting of a (meth)allyl isocyanurate compound, a (meth)allyl group-substituted nadimide compound, and a (meth)allyl compound having a glycoluril structure, further preferably contains a (meth)allyl isocyanurate compound and / or a (meth)allyl group-substituted nadimide compound, and even more preferably contains a (meth)allyl group-substituted nadimide compound.

[0167] Examples of the tri(meth)allyl cyanurate compound include tri(meth)allyl cyanurate compounds (for example, triallyl cyanurate having the structure shown below). [ka] In addition, examples of compounds containing a (meth)allyl group include resins having an allyl group described in WO 2022 / 210095 (for example, compounds described in Synthesis Examples 3, 4, 6, 20, and 22 of the same publication), the contents of which are incorporated herein by reference.

[0168] When the resin composition of the present embodiment contains a compound containing a (meth)allyl group, the molecular weight is preferably 195 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more. By making it equal to or more than the lower limit, low dielectric properties and heat resistance tend to be further improved. The molecular weight of the compound containing a (meth)allyl group is also preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, and even more preferably 800 or less. By making it equal to or less than the upper limit, low thermal expansion tends to be further improved.

[0169] When the resin composition of the present embodiment contains a compound containing a (meth)allyl group, the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the compound containing a (meth)allyl group equal to or more than the above lower limit, excellent moldability and heat resistance tend to be further improved. In addition, the upper limit of the content of the compound containing a (meth)allyl group is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the compound containing a (meth)allyl group equal to or less than the above upper limit, low thermal expansion tends to be further improved. The resin composition of the present embodiment may contain only one type of compound containing a (meth)allyl group, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0170] <<<(Meth)allyl isocyanurate compounds>>> The (meth)allyl isocyanurate compound is not particularly limited as long as it has two or more (meth)allyl groups and an isocyanurate ring (nurate skeleton). The (meth)allyl isocyanurate compound has a large number of (meth)allyl groups that serve as crosslinking points, and therefore tends to be strongly cured with the resin (A) and the polyphenylene ether compound (B) as well as other resin components, resulting in a cured product with low dielectric properties (Dk and / or Df) and excellent heat resistance. The (meth)allyl isocyanurate compound is preferably a compound represented by the formula (TA). Formula (TA) [ka] (In formula (TA), R A represents a substituent).

[0171] In formula (TA), R A represents a substituent, and is more preferably a substituent having a formula weight of 15 to 500.

[0172] R A The first example is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. By using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, a resin composition can be provided that is excellent in crosslinkability and can give a cured product having high toughness. This can prevent the resin composition from cracking during etching or the like, even if the resin composition does not contain a substrate such as glass cloth. From the viewpoint of improving handleability, the number of carbon atoms in the alkyl group and / or alkenyl group is preferably 3 or more, more preferably 8 or more, and may be 12 or more and 18 or less. This improves the resin flowability of the resin composition, and is considered to result in superior circuit filling properties when a multilayer circuit board or the like is produced using the resin composition of the present embodiment.

[0173] R A A second example of R is a group containing an allyl isocyanurate group. A When contains an allyl isocyanurate group, the compound represented by formula (TA) is preferably a compound represented by formula (TA-1). Formula (TA-1) [ka] (In formula (TA-1), R A2 is a divalent linking group.

[0174] In formula (TA-1), R A2 is preferably a divalent linking group having a formula weight of 54 to 250, more preferably a divalent linking group having a formula weight of 54 to 250 and both ends of which are carbon atoms, and further preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms (however, the aliphatic hydrocarbon group may contain an ether group or may have a hydroxyl group). A2 is preferably a group represented by any one of the following formulas (i) to (iii). [ka] (In formulas (i) to (iii), p c1 represents the number of repeating methylene units and is an integer from 2 to 18. c2 represents the number of repeating units of the oxyethylene group, which is 0 or 1. * is the bonding site.) The above p c1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and further preferably an integer of 3 to 5. The above p c2may be 0 or 1, but is preferably 1.

[0175] R A A third example is a phosphorus-based substituent.

[0176] R A2 is preferably the first example.

[0177] In this embodiment, it is preferable that the reactive group (allyl group) equivalent of the compound represented by formula (TA) is 1000 g / eq or less. If the equivalent is 1000 g / eq or less, it is considered that a high Tg can be obtained more reliably.

[0178] Examples of the alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and docosyl groups. Examples of the alkenyl group having 2 to 22 carbon atoms include allyl and decenyl groups.

[0179] Specific examples of the compound represented by formula (TA) include triallyl isocyanurate, 5-octyl-1,3-diallyl isocyanurate, 5-dodecyl-1,3-diallyl isocyanurate, 5-tetradecyl-1,3-diallyl isocyanurate, 5-hexadecyl-1,3-diallyl isocyanurate, 5-octadecyl-1,3-diallyl isocyanurate, 5-eicosyl-1,3-diallyl isocyanurate, 5-docosyl-1,3-diallyl isocyanurate, 5-decenyl-1,3-diallyl isocyanurate, etc. These may be used alone or in combination of two or more, and may be used as a prepolymer.

[0180] The method for producing the compound represented by formula (TA) is not particularly limited, but for example, the compound can be obtained by reacting diallyl isocyanurate with an alkyl halide in an aprotic polar solvent such as N,N'-dimethylformamide in the presence of a basic substance such as sodium hydroxide, potassium carbonate, or triethylamine at a temperature of about 60°C to 150°C.

[0181] In addition, the compound represented by formula (TA) may be commercially available. Commercially available compounds are not particularly limited, but include, for example, L-DAIC manufactured by Shikoku Chemical Industry Co., Ltd. and P-DAIC having a phosphorus-based substituent manufactured by Shikoku Chemical Industry Co., Ltd. Triaryl isocyanurate is, for example, TAIC manufactured by Shinryo Corporation. Compounds represented by formula (TA-1) are, for example, DD-1 manufactured by Shikoku Chemical Industry Co., Ltd.

[0182] The molecular weight of the (meth)allyl isocyanurate compound (preferably, a compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and even more preferably 500 or more. By setting the molecular weight to the above lower limit or more, the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product tend to be further improved. In addition, the molecular weight of the (meth)allyl isocyanurate compound (preferably, a compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, and even more preferably 800 or less. By setting the molecular weight to the above upper limit or less, the low thermal expansion of the obtained cured product tends to be further improved.

[0183] When the resin composition of the present embodiment contains a (meth)allyl isocyanurate compound, the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the (meth)allyl isocyanurate compound equal to or more than the above lower limit, the resin composition has excellent moldability, and the heat resistance and low thermal expansion of the obtained cured product tend to be further improved. In addition, the upper limit of the content of the (meth)allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the (meth)allyl isocyanurate compound equal to or less than the above upper limit, the heat resistance and low dielectric properties (Dk and / or Df) of the obtained cured product tend to be further improved. The resin composition of the present embodiment may contain only one type of (meth)allyl isocyanurate compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0184] <<<(Meth)allyl group-substituted nadimide compounds>>> The (meth)allyl group-substituted nadimide compound is not particularly limited as long as it has two or more (meth)allyl group-substituted nadimide groups in the molecule. Specific examples thereof include the compound represented by the following formula (AN). Formula(AN) [ka] In formula (AN), R1's each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R2's each independently represent an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by formula (AN-2) or (AN-3). Formula (AN-2) [ka] (In formula (AN-2), R3 represents a methylene group, an isopropylidene group, or a group represented by -C(=O)-, -O-, -S-, or -S(=O)2-.) Formula (AN-3) [ka] (In formula (AN-3), each R4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0185] In addition, the compound represented by formula (AN) may be a commercially available product. The commercially available products are not particularly limited, but include, for example, the compound represented by formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)) and the compound represented by formula (AN-5) (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)). These may be used alone or in combination of two or more. Formula (AN-4) [ka] Formula (AN-5) [ka]

[0186] The molecular weight of the (meth)allyl group-substituted nadimide compound (preferably a compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may be 550 or more. By making the molecular weight of the (meth)allyl group-substituted nadimide compound equal to or more than the above lower limit, the low dielectric property, low thermal expansion property, and heat resistance tend to be further improved. The molecular weight of the (meth)allyl group-substituted nadimide compound (preferably a compound represented by formula (AN)) is also preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less, and may be 700 or less, or 600 or less. By making the molecular weight of the (meth)allyl group-substituted nadimide compound equal to or less than the above upper limit, the moldability and peel strength tend to be further improved.

[0187] When the resin composition of the present embodiment contains a (meth)allyl group-substituted nadiimide compound (preferably a compound represented by formula (AN)), the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the (meth)allyl group-substituted nadiimide compound equal to or more than the above lower limit, excellent moldability, low dielectric properties, low thermal expansion properties, and heat resistance tend to be further improved. In addition, the upper limit of the content of the (meth)allyl group-substituted nadiimide compound (preferably a compound represented by formula (AN)) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the (meth)allyl group-substituted nadiimide compound equal to or less than the above upper limit, moldability and peel strength tend to be further improved. The resin composition of the present embodiment may contain only one type of (meth)allyl group-substituted nadimide compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0188] <<<(Meth)allyl compounds having glycoluril structures>>> The (meth)allyl compound having a glycoluril structure is not particularly limited as long as it is a compound containing a glycoluril structure and two or more (meth)allyl groups. When a (meth)allyl compound having a glycoluril structure is blended into a resin composition, the number of (meth)allyl groups can be increased, that is, the number of crosslinking points can be increased. Therefore, like the (meth)allyl isocyanurate compound, it tends to be firmly cured with the resin (A) and the polyphenylene ether compound (B) as well as other resin components, and to obtain a cured product having low dielectric properties (Dk and / or Df) and excellent heat resistance. In this embodiment, the (meth)allyl compound having a glycoluril structure is preferably a compound represented by formula (GU). Formula(GU) [ka] (In formula (GU), each R is independently a hydrogen atom or a substituent, and at least two R are groups containing a (meth)allyl group.) In formula (GU), each R is independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, more preferably a (meth)allyl group, and even more preferably an allyl group. In formula (GU), three or four of R are preferably groups containing a (meth)allyl group, and four of R are more preferably groups containing a (meth)allyl group.

[0189] A specific example of the compound represented by formula (GU) is 1,3,4,6-tetraallylglycoluril (a compound represented by formula (GU) in which all R's are allyl groups).

[0190] The compound represented by formula (GU) may be a commercially available product, which is not particularly limited, but may be, for example, TA-G manufactured by Shikoku Chemical Industries Co., Ltd.

[0191] The molecular weight of the (meth)allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, even more preferably 250 or more, and may be 300 or more, 400 or more. By making the molecular weight of the (meth)allyl compound having a glycoluril structure equal to or greater than the above lower limit, the heat resistance and low thermal expansion of the obtained cured product tend to be improved. The molecular weight of the (meth)allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is also preferably 1500 or less, more preferably 1000 or less, even more preferably 800 or less, and may be 700 or less, 600 or less. By making the molecular weight of the (meth)allyl compound having a glycoluril structure equal to or less than the above upper limit, the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product tend to be improved.

[0192] When the resin composition of the present embodiment contains a (meth)allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)), the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the (meth)allyl compound having a glycoluril structure equal to or more than the above lower limit, the resin composition tends to have excellent moldability, and the heat resistance and low thermal expansion of the obtained cured product tend to be further improved. In addition, the upper limit of the content of the (meth)allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the (meth)allyl compound having a glycoluril structure equal to or less than the above upper limit, the low dielectric properties (Dk and / or Df) of the obtained cured product tend to be further improved. The resin composition of the present embodiment may contain only one type of (meth)allyl compound having a glycoluril structure, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0193] <<Oxetane resin>> The resin composition of the present embodiment may contain an oxetane resin. The oxetane resin is not particularly limited as long as it is a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2), and a wide variety of compounds commonly used in the field of printed wiring boards can be used. Examples of oxetane resins include oxetane, alkyl oxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), and OXT-121 (manufactured by Toagosei Co., Ltd.).

[0194] The resin composition of the present embodiment preferably contains an oxetane resin in a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an oxetane resin, the content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peel strength and toughness of the obtained cured product tend to be improved. When the resin composition of the present embodiment contains an oxetane resin, the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the oxetane resin is 50 parts by mass or less, the electrical properties of the obtained cured product tend to be improved. The resin composition in the present embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition in this embodiment may be configured to be substantially free of oxetane resin, which means that the content of oxetane resin is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0195] <<Benzoxazine compounds>> The resin composition of the present embodiment may contain a benzoxazine compound. The benzoxazine compound is not particularly limited as long as it has two or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) dihydrobenzoxazine rings in one molecule, and a wide variety of compounds commonly used in the field of printed wiring boards can be used. Examples of the benzoxazine compound include bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.).

[0196] The resin composition of the present embodiment preferably contains a benzoxazine compound in an amount not impairing the effects of the present invention. When the resin composition of the present embodiment contains a benzoxazine compound, the content is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition. The resin composition in the present embodiment may contain only one type of benzoxazine compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may be configured to be substantially free of benzoxazine compounds, meaning that the content of the benzoxazine compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0197] <<Arylcyclobutene resin>> The resin composition of the present embodiment may contain an arylcyclobutene resin. For details, arylcyclobutene resins described in paragraph 0042 of JP2019-194312A are exemplified, the contents of which are incorporated herein by reference.

[0198] <<Polyamide resin>> The resin composition of the present embodiment may contain a polyamide resin, or may contain a thermosetting polyamide resin. For details, reference can be made to the polyamides described in paragraph 0065 of JP 2019-194312 A and the polyamides described in paragraph 0063 of JP 6951829 A, the contents of which are incorporated herein by reference.

[0199] <<Polyimide resin>> The resin composition of the present embodiment may contain a polyimide resin, or may contain a thermosetting polyimide resin. For details, reference can be made to the polyimides and the like described in paragraphs 0063 to 0064 of Japanese Patent No. 6951829, the contents of which are incorporated herein by reference.

[0200] <<Perfluorovinyl ether resin>> The resin composition of the present embodiment may contain a perfluorovinyl ether resin, or may contain a perfluorovinyl benzyl ether resin. For details, the perfluorovinyl ether resin described in paragraph 0043 of JP2019-194312A is exemplified, the contents of which are incorporated herein by reference.

[0201] <<Polyphenylene ether compounds having terminal carbon-carbon unsaturated double bonds and compounds having a styrene group other than styrene resins, represented by the formula (T-St)>> The resin composition of the present embodiment may contain a polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond and a compound having a styrene group other than a styrene resin, represented by the formula (T-St). Details of these include compounds having styrene at the end described in International Publication No. 2022 / 210095 (for example, the compounds described in Synthesis Examples 12 to 16 in the same publication), the descriptions in paragraphs 0029 to 0038 of JP-A-2022-85610, and the vinyl benzyl ether resin described in paragraph 0041 of JP-A-2019-194312, the contents of which are incorporated herein by reference.

[0202] <<Compounds having an isopropenyl group other than the resin represented by formula (T)>> The resin composition of the present embodiment may contain a compound having an isopropenyl group other than the resin represented by formula (T). For details, the resin having an isopropenyl group described in WO 2022 / 210095 (for example, the compounds described in Synthesis Examples 1, 2, 7, and 8 in the same publication) is exemplified, the contents of which are incorporated herein by reference.

[0203] <<Polyfunctional (meth)acrylate compounds other than the polyphenylene ether compounds having terminal carbon-carbon unsaturated double bonds>> The resin composition of the present embodiment may contain a polyfunctional (meth)acrylate compound other than the polyphenylene ether compound having a terminal carbon-carbon unsaturated double bond. Here, the polyfunctional (meth)acrylate compound means a compound containing two or more (meth)acryloyloxy groups in one molecule, and preferably contains three or more (meth)acryloyloxy groups in one molecule. The polyfunctional (meth)acrylate compound is preferably a compound having 3 to 5 (meth)acryloyloxy groups, more preferably a compound having 3 or 4 (meth)acryloyloxy groups, and even more preferably a compound having 3 (meth)acryloyloxy groups. The (meth)acrylate compound is preferably a compound having a methacryloyloxy group. Since the polyfunctional (meth)acrylate compound has a large number of (meth)acrylate groups that serve as crosslinking points, it is strongly cured with other resin components, and a cured product having low dielectric properties (Dk and / or Df) and excellent heat resistance is obtained. As the polyfunctional (meth)acrylate compound, a compound represented by formula (MA) is preferable. Formula(MA) [ka] (In formula (MA), R 1 represents a hydrogen atom or a substituent, R 2 each independently represents a hydrogen atom or a methyl group.

[0204] In formula (MA), R 1represents a hydrogen atom or a substituent, and is more preferably a substituent having a formula weight of 15 to 500, more preferably a substituent having a formula weight of 15 to 300, even more preferably a substituent having a formula weight of 15 to 100, and even more preferably a substituent having a formula weight of 15 to 50.

[0205] R 1 is preferably a hydrocarbon group or a (meth)acryloyloxy group, more preferably a hydrocarbon group having 22 or less carbon atoms, and even more preferably an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms. By using a compound having an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, it is possible to provide a resin composition which is excellent in crosslinkability and can give a cured product having high toughness. As a result, even if the resin composition does not contain a substrate such as glass cloth, it is possible to suppress cracking during etching treatment or the like. From the viewpoint of improving handleability, the number of carbon atoms in the alkyl group and / or alkenyl group is preferably 2 or more, and may be 8 or more, or may be 12 or more and 18 or less. This improves the resin flow property of the resin composition, and is considered to improve the circuit filling property when a multilayer circuit board or the like is produced using the resin composition of the present embodiment.

[0206] In this embodiment, the (meth)acrylic group equivalent of the compound represented by formula (MA) is preferably 1000 g / eq or less. If the equivalent is 1000 g / eq or less, a high Tg tends to be obtained more reliably. The lower limit of the (meth)acrylic group equivalent is, for example, 99 g / eq or more.

[0207] The alkyl group having 1 to 22 carbon atoms is preferably a linear alkyl group having 1 to 22 carbon atoms or a branched alkyl group having 3 to 22 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, etc. The alkenyl group having 2 to 22 carbon atoms is preferably an alkenyl group having 2 to 15 carbon atoms, such as an allyl group, a decenyl group, etc.

[0208] Specific examples of the compound represented by formula (MA) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, etc. These may be used alone or in combination of two or more, or may be used as a prepolymer.

[0209] In addition, the compound represented by formula (MA) may be a commercially available product. Although there is no particular limitation on commercially available products, for example, trimethylolpropane trimethacrylate, such as "NK Ester TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd., may be used.

[0210] The molecular weight of the polyfunctional (meth)acrylate compound is preferably 300 or more, more preferably 330 or more, and may be 400 or more, or may be 500 or more. By making the molecular weight equal to or greater than the lower limit, the low dielectric properties (Dk and / or Df) and heat resistance of the obtained cured product tend to be improved. In addition, the molecular weight of the (meth)acrylate compound (preferably, the compound represented by formula (MA)) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, and even more preferably 800 or less. By making the molecular weight equal to or less than the upper limit, the low thermal expansion of the obtained cured product tends to be improved.

[0211] For details, the resins having a (meth)acrylic group described in International Publication No. 2022 / 210095 (for example, the compounds described in Synthesis Examples 5 and 21 of the same publication) and the resins having a (meth)acrylic group described in Japanese Patent No. 6962507 (for example, the compounds described in Examples 1 to 9) are exemplified, the contents of which are incorporated herein by reference.

[0212] When the resin composition of the present embodiment contains a polyfunctional (meth)acrylate compound, the content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and may be 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the polyfunctional (meth)acrylate compound equal to or more than the above lower limit, the resin composition has excellent moldability, and the heat resistance and low thermal expansion of the obtained cured product tend to be further improved. In addition, the upper limit of the content of the (meth)acrylate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and may be 20 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content of the polyfunctional (meth)acrylate compound equal to or less than the above upper limit, the heat resistance and low dielectric properties (Dk and / or Df) of the obtained cured product tend to be further improved. The resin composition of the present embodiment may contain only one type of polyfunctional (meth)acrylate compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0213] <<Elastomer>> The resin composition of the present embodiment may contain an elastomer. The elastomer may be thermoplastic, thermosetting, or neither thermoplastic nor thermosetting, but is preferably thermoplastic. The elastomer in the present embodiment is not particularly limited, and examples thereof include at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof. Further, examples of the elastomer include oligomers or polymers having a curable vinyl functional group, and polybutadiene resins described in paragraphs 0044 and 0045 of JP 2019-194312 A, the contents of which are incorporated herein by reference.

[0214] The number average molecular weight of the elastomer (preferably a thermoplastic elastomer) used in this embodiment is preferably 1000 or more. By making the number average molecular weight 1000 or more, the low dielectric properties (Dk and / or Df, particularly low dielectric tangent) of the obtained cured product tend to be more excellent. The number average molecular weight is preferably 1500 or more, more preferably 2000 or more, and may be 600,000 or more, 700,000 or more, or 800,000 or more depending on the application. The upper limit of the number average molecular weight of the elastomer is preferably 400,000 or less, more preferably 350,000 or less, and even more preferably 300,000 or less. By making it equal to or less than the upper limit, the solubility of the elastomer component in the resin composition tends to be improved. When the resin composition of the present embodiment contains two or more types of elastomers, it is preferable that the number average molecular weight of the mixture thereof falls within the above range.

[0215] The elastomer used in this embodiment may be a resin containing a polybutadiene structure. The polybutadiene structure may be partially or entirely hydrogenated. Specific examples include B-1000, B-2000, B-3000, BI-2000, and BI-3000 manufactured by Nippon Soda Co., Ltd., and Ricon 100, Ricon 130, Ricon 131, Ricon 142, Ricon 150, Ricon 181, and Ricon 184 manufactured by CRAY VALLEY.

[0216] The elastomer used in this embodiment is a resin containing a poly(meth)acrylate structure. Specific examples include Teisan Resin manufactured by Nagase ChemteX Corporation, ME-2000, W-197C, KG-15, and KG-3000 manufactured by Negami Chemical Industries, Ltd.

[0217] The elastomer used in this embodiment may be a resin containing a polycarbonate structure. A resin containing a polycarbonate structure may be called a "polycarbonate resin". Examples of such resins include carbonate resins that do not have a reactive group, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and epoxy group-containing carbonate resins. The reactive group here refers to a functional group that can react with other components, such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group. Specific examples of polycarbonate resins include FPC0220 and FPC2136 manufactured by Mitsubishi Gas Chemical Company, Inc., and T6002 and T6001 (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation.

[0218] The elastomer used in this embodiment is a resin containing a polysiloxane structure, specific examples of which include SMP-2006, SMP-2003PGMEA, SMP-5005PGMEA, KR-510, and SMP-7014-3S manufactured by Shin-Etsu Silicones Co., Ltd.

[0219] The elastomer used in the present embodiment may be a resin containing a polyalkylene structure and / or a polyalkyleneoxy structure. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the resin containing a polyalkylene structure and / or a polyalkyleneoxy structure include PTXG-1000 and PTXG-1800 manufactured by Asahi Kasei Fibers Corporation.

[0220] The elastomer used in this embodiment is a resin containing a polyisoprene structure, specific examples of which include KL-610 and KL613 manufactured by Kuraray Co., Ltd.

[0221] The elastomer used in this embodiment is a resin containing a polyisobutylene structure. Specific examples include SIBSTAR-073T (styrene-isobutylene-styrene triblock copolymer) and SIBSTAR-042D (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0222] In this embodiment, the elastomer is preferably an elastomer containing a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "elastomer (e)"). By using such an elastomer (e), the low dielectric properties (Dk and / or Df, particularly low dielectric tangent) of the obtained cured product are more excellent.

[0223] The elastomer (e) contains a styrene monomer unit. By containing a styrene monomer unit, the solubility of the elastomer (e) in the resin composition is improved. Examples of the styrene monomer include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoints of availability and productivity. Among these, styrene is particularly preferred. The content of the styrene monomer unit in the elastomer (e) is preferably in the range of 10 to 50% by mass of the total monomer units, more preferably in the range of 13 to 45% by mass, and even more preferably in the range of 15 to 40% by mass. If the content of the styrene monomer unit is 50% by mass or less, the adhesion and tackiness to the substrate and the like will be better. Also, if it is 10% by mass or more, the adhesion can be suppressed, adhesive residue and stop marks are unlikely to occur, and the adhesive surfaces tend to be easily peeled from each other, which is preferable. The elastomer (e) may contain only one type of styrene monomer unit, or may contain two or more types. When it contains two or more types, the total amount is preferably within the above range. The method for measuring the content of the styrene monomer unit in the elastomer (e) of this embodiment can be found in International Publication No. 2017 / 126469, the contents of which are incorporated herein by reference. The same applies to the conjugated diene monomer unit and the like described below.

[0224] The elastomer (e) contains a conjugated diene monomer unit. The inclusion of the conjugated diene monomer unit improves the solubility of the elastomer (e) in the resin composition. The conjugated diene monomer is not particularly limited as long as it is a diolefin having a pair of conjugated double bonds. Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred. The elastomer (e) may contain only one type of conjugated diene monomer unit, or may contain two or more types.

[0225] In the above elastomer (e), the mass ratio of the styrene monomer units to the conjugated diene monomer units is preferably in the range of 5 / 95 to 80 / 20, more preferably in the range of 7 / 93 to 77 / 23, and even more preferably in the range of 10 / 90 to 70 / 30. If the mass ratio of the styrene polymer units to the conjugated diene monomer units is in the range of 5 / 95 to 80 / 20, the adhesion can be suppressed from increasing, the adhesion strength can be maintained high, and the adhesive surfaces can be easily peeled from each other.

[0226] The conjugated diene bonds of the elastomer (e) may be entirely hydrogenated, partially hydrogenated, or not hydrogenated.

[0227] The elastomer (e) may or may not contain other monomer units in addition to the styrene monomer units and the conjugated diene monomer units. Examples of other monomer units include aromatic vinyl compound units other than the styrene monomer units. In the above elastomer (e), the sum of styrene monomer units and conjugated diene monomer units preferably accounts for 90 mass% or more of all monomer units, more preferably 95 mass% or more, even more preferably 97 mass% or more, and still more preferably 99 mass% or more. As described above, the elastomer (e) may contain only one type of styrene monomer unit and one type of conjugated diene monomer unit, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range.

[0228] The elastomer (e) used in the present embodiment may be a block polymer or a random polymer. In addition, it may be a hydrogenated elastomer in which the conjugated diene monomer unit is hydrogenated, an unhydrogenated elastomer in which the conjugated diene monomer unit is not hydrogenated, or a partially hydrogenated elastomer in which the conjugated diene monomer unit is partially hydrogenated. The unhydrogenated elastomer or the partially hydrogenated elastomer is preferable. In one embodiment of this embodiment, the elastomer (e) is a hydrogenated elastomer. Here, the hydrogenated elastomer means, for example, an elastomer in which double bonds based on conjugated diene monomer units in the elastomer are hydrogenated, and includes elastomers with a hydrogenation rate (hydrogenation rate) of 100% or more as well as elastomers with a hydrogenation rate of 80% or more. The hydrogenation rate in the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. In this embodiment, the hydrogenation rate is 1 It is calculated from the results of H-NMR spectroscopy. In one embodiment of this embodiment, the elastomer (e) is an unhydrogenated elastomer. Here, the unhydrogenated elastomer refers to an elastomer in which the ratio of hydrogenated double bonds based on conjugated diene monomer units in the elastomer, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. The hydrogenation rate is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less. On the other hand, a partially hydrogenated elastomer means an elastomer in which some of the double bonds based on the conjugated diene monomer units in the elastomer are hydrogenated, and usually refers to an elastomer in which the hydrogenation rate (hydrogenation rate) is less than 80% and more than 20%.

[0229] Examples of commercially available elastomers (e) used in the present embodiment include SEPTON (registered trademark) 2104, V9461, and S8104 manufactured by Kuraray Co., Ltd., SOE (registered trademark) S1606, S1613, S1609, and S1605 manufactured by Asahi Kasei Corporation, Tuftec (registered trademark) H1041, H1043, P2000, and MP10 manufactured by Asahi Kasei Corporation, and DYNARON (registered trademark) 9901P and TR2250 manufactured by JSR Corporation.

[0230] The elastomer used in this embodiment may also be a liquid diene. The liquid diene refers to a liquid elastomer containing a conjugated diene monomer unit. Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, with 1,3-butadiene and isoprene being preferred, and 1,3-butadiene being more preferred. Examples of the liquid diene used in this embodiment include liquid polybutadiene, liquid polyisoprene, modified liquid polybutadiene, modified liquid polyisoprene, liquid acrylonitrile-butadiene copolymer, and liquid styrene-butadiene copolymer. The number average molecular weight of the liquid diene is not particularly limited as long as it is liquid at 20° C., but is preferably 500 or more and 10,000 or less.

[0231] When the resin composition of the present embodiment contains an elastomer (preferably, elastomer (e)), the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition, and may be 10 parts by mass or more, 12 parts by mass or more, depending on the application, etc. By making it equal to or more than the lower limit, the dielectric characteristics (low dielectric tangent) tend to be further improved. In addition, the upper limit of the content of the elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 32 parts by mass or less, and even more preferably 28 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making it equal to or less than the upper limit, the heat resistance tends to be further improved. The resin composition of the present embodiment may contain only one type of elastomer, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition in this embodiment may be configured to be substantially free of elastomer, which means that the content of elastomer is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0232] <<Petroleum resin>> The resin composition of the present embodiment may contain a petroleum resin. By containing a petroleum resin, the melt viscosity can be reduced. Petroleum resins are resins obtained by pyrolyzing petroleum naphtha to extract necessary fractions, and then polymerizing the remaining components without isolating unsaturated hydrocarbons, or in the presence of a catalyst. The remaining fractions are mainly fractions containing C5 fractions (isoprene, piperylene, cyclopentadiene, pentenes, pentanes, etc.) or C9 fractions (vinyltoluene, indene, dicyclopentadiene, etc.).

[0233] The catalyst used in the production of petroleum resin is preferably an acid catalyst.Specifically, boron trifluoride phenol complex, boron trifluoride ether complex, Lewis acid such as aluminum chloride, aluminum bromide, iron (III) chloride, iron (III) bromide, solid acid such as zeolite, silica, montmorillonite, alumina, ion exchange resin such as sulfonic acid group-containing fluororesin, sulfonic acid group-containing polystyrene resin, protonic acid such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, oxalic acid, nitric acid, paratoluenesulfonic acid, trifluoroacetic acid, etc. can be used.Among these, it is preferable to use Lewis acid or solid acid, which is unlikely to cause side reactions and has a high reaction rate, and various complexes of boron trifluoride and aluminum chloride are more preferable in terms of ease of availability and high reactivity.

[0234] The weight average molecular weight of the petroleum resin is not particularly limited, but is preferably 500 to 10,000, more preferably 500 to 5,000. By making it equal to or less than the upper limit, compatibility with other resins tends to be improved, and solubility in solvents also tends to be increased. By making it equal to or more than the lower limit, the heat resistance and mechanical strength of the obtained cured product tends to be improved.

[0235] Although the softening point of the petroleum resin is not particularly limited, it is preferable that it is high, and is preferably 80° C. or higher, and more preferably 100° C. or higher. By making it equal to or higher than the lower limit, the heat resistance of the obtained cured product tends to be improved.

[0236] Examples of the petroleum resin include aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and dicyclopentadiene petroleum resins, with dicyclopentadiene petroleum resins being preferred. Examples of dicyclopentadiene-based petroleum resins include resins obtained by polymerizing dicyclopentadiene-based fractions such as dicyclopentadiene, isopropenylnorbornene, dimethyldicyclopentadiene, and tricyclopentadiene, and resins obtained by polymerizing dicyclopentadiene-based fractions and other monomers having unsaturated bonds, preferably unsaturated cyclic olefins.

[0237] Examples of the unsaturated cyclic olefins include cyclopentadiene; norbornene monomers such as 2-norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenylnorbornene, 5-propenyl-2-norbornene, and 5-ethylidene-2-norbornene; and further examples of norbornene monomers having three or more rings include tricyclic monomers other than dicyclopentadiene fractions such as diethyldicyclopentadiene and dihydrodicyclopentadiene, tetracyclic monomers such as tetracyclododecene, pentacyclic monomers such as tricyclopentadiene, heptacyclic monomers such as tetracyclopentadiene, and alkyl-, alkylidene-, and aryl-substituted monomers of these polycyclic monomers. Examples of the alkyl substituted polycyclic rings include methyl, ethyl, propyl, and butyl substituted rings, and examples of the alkylidene substituted polycyclic rings include ethylidene substituted rings, and examples of the aryl substituted polycyclic rings include phenyl, tolyl, and naphthyl substituted rings.

[0238] Furthermore, as a monomer having an unsaturated bond other than the unsaturated cyclic olefins, an olefin having 3 to 12 carbon atoms may be copolymerized, and examples thereof include α-olefins such as propylene, butene-1, pentene-1, 1,3-pentadiene, hexene-1, heptene-1, octene-1, diisobutene, nonene-1, decene-1, 4-phenylbutene-1, 6-phenylhexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylpentene-1, 3-methylhexene-1, 4-methylhexene-1, 5-methylhexene-1, 3,3-dimethylpentene-1, 3,4-dimethylpentene-1, 4,4-dimethylpentene-1, vinylcyclohexane, and vinylcyclohexene; and halogen-substituted α-olefins such as hexafluoropropene, 2-fluoropropene, 3-fluoropropene, and 3,4-dichlorobutene-1.

[0239] Examples of monomers having an unsaturated bond other than those mentioned above include ethylene, tetrafluoroethylene, fluoroethylene, 1,1-difluoroethylene, trifluoroethylene; alkyl styrenes such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, and pt-butylstyrene; halogenated styrenes such as p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, and o-methyl-p-fluorostyrene; maleic anhydride, maleic acid, fumaric acid, allyl alcohol, 3-buten-2-ol, methylbuten-1-ol, vinyl acetate, and vinyl chloride.

[0240] The above monomers may be used alone or in combination of two or more kinds.

[0241] The petroleum resin may be commercially available. Examples of aliphatic petroleum resins include Quinton A100, Quinton B170, Quinton K100, Quinton M100, Quinton R100, and Quinton C200S manufactured by Zeon Co., Ltd., and Marucaretz T-100AS and Marucaretz R-100AS manufactured by Maruzen Petrochemical Co., Ltd. Examples of aromatic petroleum resins include Neopolymer L-90, Neopolymer 120, and Neopolymer 20 manufactured by JXTG Nippon Oil & Energy Corporation. Polymer 130, Neopolymer 140, Neopolymer 150, Neopolymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer 130S, Neopolymer S, Tosoh Corporation's Petcol LX, Petcol LX-HS, Petcol 100T, Petcol 120, Petcol 120HS, Petcol 130, Petcol 140, Petcol 140HM, Petcol 140HM5, Petcol 150, Petcol Coal 150AS, copolymerized petroleum resins include Quinton D100, Quinton N180, Quinton P195N, Quinton S100, Quinton S195, Quinton U185, Quinton G100B, Quinton G115, Quinton D200, Quinton E200SN, and Quinton N295 manufactured by Zeon Co., Ltd., and Petrotac 60, Petrotac 70, Petrotac 90, Petrotac 90V, and Petrotac 100 manufactured by Tosoh Corporation. , Petrotac 100V, Petrotac 90HM, and DCPD (dicyclopentadiene)-based petroleum resins include Maruzen Petrochemical Co., Ltd.'s MARUKAREZ M-890A and MARUKAREZ M-845A, Nippon Zeon Co., Ltd.'s Quinton 1325, Quinton 1345, Quinton 1500, Quinton 1525L, and Quinton 1700, and ENEOS Corporation's HA085, HA103, HA105, HA125, HB103, and HB125. Moreover, as the petroleum resin, those described in Organic Synthesis Chemistry, Vol. 25, No. 6 (1967) can also be used.

[0242] When the resin composition of the present embodiment contains a petroleum resin, the lower limit of the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making it equal to or more than the lower limit, the melt viscosity tends to decrease. In addition, the upper limit of the content of the petroleum resin is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and may be 40 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making it equal to or less than the upper limit, Df tends to decrease. The resin composition in the present embodiment may contain only one type of petroleum resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. The resin composition in the present embodiment may be configured to be substantially free of petroleum resin, which means that the content of petroleum resin is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0243] <Filling material (D)> The resin composition of the present embodiment preferably contains a filler (D). By containing the filler (D), the physical properties such as low dielectric properties (Dk and / or Df), flame resistance, and low thermal expansion of the resin composition and its cured product can be further improved. Moreover, the filler (D) used in this embodiment is more preferably excellent in low dielectric properties (Dk and / or Df). For example, the filler (D) used in this embodiment has a relative dielectric constant (Dk) of preferably 8.0 or less, more preferably 6.0 or less, and even more preferably 4.0 or less at a frequency of 10 GHz measured according to the cavity resonator perturbation method. The lower limit of the relative dielectric constant is, for example, 2.0 or more. The filler (D) used in this embodiment has a dielectric loss tangent (Df) of preferably 0.05 or less, more preferably 0.01 or less at a frequency of 10 GHz measured according to the cavity resonator perturbation method. The lower limit of the dielectric loss tangent is, for example, 0.0001 or more.

[0244] The filler (D) used in this embodiment is not particularly limited in type, and fillers generally used in the art can be suitably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica, metal oxides such as alumina, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide, composite oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, and calcium titanate, nitrides such as boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride, aluminum hydroxide, aluminum hydroxide heat-treated products (aluminum hydroxide that has been heat-treated to remove a portion of the water of crystallization), boehmite, and metal hydroxides (including hydrates) such as magnesium hydroxide, monooxides, and the like. Examples of fillers include inorganic fillers such as molybdenum compounds such as barium sulfate and zinc molybdate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, NER-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass, as well as organic fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell type rubber powders, silicone resin powder, silicone rubber powder, and silicone composite powder. In this embodiment, inorganic fillers are preferred, and more preferably contain one or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate, and from the viewpoint of low dielectric properties (Dk and / or Df), more preferably contain one or more selected from the group consisting of silica and aluminum hydroxide, and even more preferably contain silica. By using these inorganic fillers, the properties such as heat resistance, low dielectric properties (Dk and / or Df), thermal expansion properties, dimensional stability, and flame retardancy of the cured product of the resin composition are further improved.

[0245] The content of the filler (D) in the resin composition of this embodiment can be appropriately set according to the desired properties, and is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By setting it to the lower limit or more, the heat resistance, low thermal expansion property, and dielectric loss tangent of the obtained cured product tend to be further improved. In addition, the upper limit of the content of the filler (D) is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 300 parts by mass or less, even more preferably 250 parts by mass or less, and may be 200 parts by mass or less, or 120 parts by mass or less, relative to 100 parts by mass of the resin solid content. By setting it to the upper limit or less, the moldability of the resin composition tends to be further improved. In the resin composition of this embodiment, one preferred embodiment is one in which the content of the filler (D) is 30% by mass to 90% by mass of the components excluding the solvent. The resin composition of the present embodiment may contain only one type of filler (D), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0246] In the resin composition of the present embodiment, when the filler (D), particularly an inorganic filler, is used, a silane coupling agent may be further included. By including a silane coupling agent, the dispersibility of the filler (D) and the adhesive strength between the resin component and the filler (D) and the substrate described below tend to be further improved. The silane coupling agent is not particularly limited, and includes silane coupling agents generally used for surface treatment of inorganic substances, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), vinylsilane compounds (e.g., vinyltrimethoxysilane, etc.), styrylsilane compounds, acrylicsilane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, etc. The silane coupling agents are used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the resin solid content.

[0247] <Monomer or oligomer having an ethylenically unsaturated group> In order to enhance the thermosetting property and the curability by active energy rays (for example, photocurability by ultraviolet rays, etc.), the resin composition of this embodiment can be used in combination with a monomer or oligomer having an ethylenically unsaturated group. The oligomer or monomer having an ethylenically unsaturated group used in this embodiment is not particularly limited as long as it is an oligomer or monomer having one or more ethylenically unsaturated groups in one molecule, but examples thereof include monomers or oligomers having a vinyl group, an isopropenyl group, an allyl group, a (meth)acryloyl group, etc., and a monomer or oligomer having a vinyl group is preferred. In this specification, a compound which corresponds to a monomer or oligomer having an ethylenically unsaturated group and which also corresponds to the polyphenylene ether compound (B) is referred to as the polyphenylene ether compound (B).

[0248] More specifically, the monomer having an ethylenically unsaturated group may be a compound (F1) (compound (F1)) having a molecular weight of less than 1,000 and containing one organic group containing an ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond constituting the organic group containing the ethylenically unsaturated bond does not include those contained as part of an aromatic ring. On the other hand, the ethylenically unsaturated bond contained as part of a non-aromatic ring is included. An example of an ethylenically unsaturated bond contained as part of a non-aromatic ring is a cyclohexenyl group in a molecule. In addition, the ethylenically unsaturated bond is also included in the part other than the terminal of a linear or branched organic group, that is, the ethylenically unsaturated bond contained in a linear or branched chain. The organic group containing an ethylenically unsaturated bond is more preferably one selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryl group, and is even more preferably a vinyl group. In addition, in this specification, a compound which is a monomer or oligomer having an ethylenically unsaturated group and which also corresponds to a silane coupling agent is referred to as a silane coupling agent.

[0249] The compound (F1) used in the present embodiment is preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and silicon atoms, more preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, and silicon atoms, and even more preferably composed only of atoms selected from carbon atoms, hydrogen atoms, oxygen atoms, and oxygen atoms. The compound (F1) used in this embodiment may or may not have a polar group. It is preferable that the compound (F1) used in this embodiment does not have a polar group. Examples of the polar group include an amino group, a carboxyl group, a hydroxyl group, and a nitro group.

[0250] In this embodiment, the molecular weight of the compound (F1) is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more. By making it equal to or more than the lower limit, there is a tendency that the volatilization of the compound (F1) from the resin composition of this embodiment or its cured product can be suppressed. The upper limit of the molecular weight of the compound (F1) is preferably 500 or less, more preferably 400 or less, even more preferably 300 or less, even more preferably 200 or less, and may be 150 or less. By making it equal to or less than the upper limit, there is a tendency that the effect of increasing the reactivity with other resin components is further improved. When the resin composition of the present embodiment contains two or more types of compound (F1), it is preferable that the average molecular weight value of the compound (F1) falls within the above range, and it is more preferable that the molecular weight of each compound falls within the above preferred range.

[0251] In this embodiment, the boiling point of the compound (F1) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. By making it equal to or higher than the lower limit, the volatilization of the compound (F1) during thermal curing of the resin composition is suppressed, and the compound (F1) can react with other curable compounds (C). The boiling point of the compound (F1) is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. By making it equal to or lower than the upper limit, it is possible to make it difficult for the compound (F1) to remain as a residual solvent in the cured product. When the resin composition of the present embodiment contains two or more types of compound (F1), it is sufficient that the average boiling point falls within the above range, but it is preferable that the boiling point of each compound falls within the above preferred range.

[0252] Examples of the compound (F1) include (meth)acrylic acid ester compounds, aromatic vinyl compounds (preferably styrene-based compounds), isopropenyl group-containing compounds, saturated fatty acid vinyl compounds, vinyl cyanide compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, ethylenically unsaturated dicarboxylic acid monoalkyl esters, ethylenically unsaturated carboxylic acid amides, unsaturated polyester compounds based on maleic anhydride, fumaric acid, itaconic acid, and citraconic acid; unsaturated epoxy (meth)acrylate compounds containing an acryloyl group or a methacryloyl group; unsaturated epoxy (meth)acrylate compounds containing a vinyl group or a (meth)allyl group; Examples of the compound include saturated epoxy compounds, urethane (meth)acrylate compounds, polyether (meth)acrylate compounds, polyalcohol (meth)acrylate compounds, alkyd acrylate compounds, polyester acrylate compounds, spiroacetal acrylate compounds, diallyl phthalate compounds, diallyl tetrabromophthalate compounds, diethylene glycol bisallyl carbonate, and polyethylene polythiol. At least one selected from the group consisting of (meth)acrylic acid ester compounds, aromatic vinyl compounds, and saturated fatty acid vinyl compounds is preferred, and aromatic vinyl compounds are more preferred. Specific examples of the compound (F1) include methylstyrene (e.g., 4-methylstyrene), ethylvinylbenzene, diethyl 4-vinylbenzylphosphonate, 4-vinylbenzyl glycidyl ether, α-methylstyrene, etc. Specific examples of the compound (F1) include the descriptions in paragraphs 0046 and 0049 of JP 2019-194312 A, the contents of which are incorporated herein by reference.

[0253] On the other hand, the resin composition according to the present embodiment preferably contains a styrene oligomer (F2) in order to improve low dielectric constant and low dielectric loss tangent. The styrene oligomer (F2) according to the present embodiment is preferably obtained by polymerizing at least one selected from the group consisting of styrene, the above-mentioned styrene derivatives, and vinyltoluene. The number average molecular weight of the styrene oligomer (F2) is preferably 178 or more, and preferably 1600 or less. In addition, the styrene oligomer (F2) is preferably a compound having an average aromatic ring number of 2 to 14, a total amount of the aromatic ring numbers of 2 to 14 being 50 mass% or more, and a boiling point of 300°C or more, and having no branched structure.

[0254] Examples of the styrene oligomer (F2) used in this embodiment include styrene polymer, vinyl toluene polymer, α-methylstyrene polymer, vinyl toluene-α-methylstyrene polymer, styrene-α-styrene polymer, etc. As the styrene polymer, a commercially available product may be used, for example, Picolastic A5 (manufactured by Eastman Chemical Co.), Picolastic A-75 (manufactured by Eastman Chemical Co.), Picotex 75 (manufactured by Eastman Chemical Co.), FTR-8100 (manufactured by Mitsui Chemical Co.), and FTR-8120 (manufactured by Mitsui Chemical Co.). In addition, an example of the vinyl toluene-α-methylstyrene polymer is Picotex LC (manufactured by Eastman Chemical Co.). Examples of the α-methylstyrene polymer include Crystallex 3070 (manufactured by Eastman Chemical Co.), Crystallex 3085 (manufactured by Eastman Chemical Co.), Crystallex (3100), Crystallex 5140 (manufactured by Eastman Chemical Co.), FMR-0100 (manufactured by Mitsui Chemical Co.), and FMR-0150 (manufactured by Mitsui Chemical Co.). Examples of the styrene-α-styrene polymer include FTR-2120 (manufactured by Mitsui Chemical Co.). These styrene oligomers may be used alone or in combination of two or more kinds. In the resin composition of the present embodiment, α-methylstyrene oligomer is preferred because it is well thermoset, has good embedding properties for fine wiring, solder heat resistance, low relative dielectric constant, and low dielectric loss tangent.

[0255] In addition, the resin composition according to this embodiment preferably contains a divinyl compound (F3) as a monomer having an ethylenically unsaturated group in order to improve the low dielectric constant and the low dielectric loss tangent. The divinyl compound is a low molecular weight compound having two vinyl groups. The two vinyl groups provide a good crosslinking density that is not too high, and as a result, the free volume of the molecule is increased, so that the dielectric loss tangent (Df) of the resulting cured product can be kept small. Furthermore, since the divinyl compound (F3) is used as a substitute for the resin (A), the polyphenylene ether compound (B), and part of the other resin component (D), the reduction in the content of the component having a polar group is also considered to contribute to the reduction of the dielectric loss tangent (Df). In addition, since both of the functional groups of the divinyl compound are vinyl groups, the reactivity with the resin (A) and the polyphenylene ether compound (B) is good, and as a result, it is considered that the heat resistance tends to be easily improved. The divinyl compound (F3) here refers to one having a molecular weight of less than 600, preferably 300 or less, and more preferably less than 195. The lower limit of the molecular weight is practically 54. Examples of the divinyl compound (F3) include divinylbenzene, 1-ethynyl-4-[2-(4-ethynylphenyl)ethyl]benzene (BVPE), , 1,3-vinyltetramethylsiloxane, and the like.

[0256] In addition, 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene are also preferably used as the monomer or oligomer having an ethylenically unsaturated group. For details of the monomer or oligomer having an ethylenically unsaturated group, see paragraphs 0069 to 0087 of WO 2017 / 135168 and paragraphs 0065 to 0067 of WO 2019 / 230945, the contents of which are incorporated herein by reference.

[0257] When the resin composition of the present embodiment contains a monomer or oligomer having an ethylenically unsaturated group, the content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content equal to or more than the lower limit, the low dielectric properties (Dk and / or Df) of the obtained cured product tend to be further improved. In addition, the upper limit of the content of the monomer or oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By making the content equal to or less than the upper limit, the heat resistance of the obtained cured product tends to be further improved. In addition, the low dielectric constant, low dielectric loss tangent, and chemical resistance tend to be further improved. The resin composition of the present embodiment may contain only one type of monomer or oligomer having an ethylenically unsaturated group, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0258] <Flame retardants> The resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and silicone-based flame retardants, and phosphorus-based flame retardants are preferred. As the flame retardant, known ones can be used, for example, halogen-based flame retardants such as brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth)acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, and chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate, and cresyl diphenyl phosphe phosphorus-based flame retardants such as phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl)phosphate, phosphazene, 1,3-phenylenebis(2,6-dixylenyl phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, and antimony trioxide, and silicone-based flame retardants such as silicone rubber and silicone resin. Among these, 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferred in this embodiment because it does not impair the low dielectric properties (Dk and / or Df) of the resulting cured product.

[0259] When the resin composition of the present embodiment contains a flame retardant, the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. The lower limit of the content of the flame retardant is preferably 30 parts by mass or less, more preferably 25 parts by mass or less. The flame retardants may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0260] <Active ester compounds> The resin composition of the present embodiment may contain an active ester compound. The active ester compound is not particularly limited, and for example, the description in paragraphs 0064 to 0066 of International Publication No. 2021 / 172317 can be referred to, the contents of which are incorporated herein by reference.

[0261] When the resin composition of the present embodiment contains an active ester compound, the amount thereof is preferably 1 part by mass or more and 90 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition. The resin composition in the present embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition in the present embodiment may be configured to be substantially free of an active ester compound, which means that the content of the active ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0262] <Dispersant> The resin composition of the present embodiment may contain a dispersant. As the dispersant, those generally used for paints can be suitably used, and the type is not particularly limited. As the dispersant, a copolymer-based wetting dispersant or a fluorine-based dispersant containing fluorine is preferably used. Specific examples of the dispersant include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark)-W996, W9010, W903, and W940 manufactured by BYK Japan Co., Ltd., Futergent manufactured by Neos Co., Ltd., and MPT manufactured by Mitsubishi Pencil Co., Ltd.

[0263] When the resin composition of the present embodiment contains a dispersant, the lower limit of the content is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and may be 0.3 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. The dispersant may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0264] <Curing accelerator> The resin composition of the present embodiment may further include a curing accelerator. The curing accelerator is not particularly limited, but examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, bis(1-methyl-1-phenylethyl)peroxide, di-t-butyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3; azo compounds such as azobisnitrile (e.g., azobisisobutyronitrile); N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, toluidine, and the like. tertiary amines such as tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, and catechol; high-temperature decomposition type radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, manganese octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; compounds obtained by dissolving these organic metal salts in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyl tins, and alkyl tin oxides. The curing accelerator is preferably at least one selected from the group consisting of imidazoles, organic peroxides, and organic metal salts, and more preferably at least one selected from the group consisting of imidazoles and organic metal salts. In the present embodiment, the composition may be configured to be substantially free of polymerization initiators such as organic peroxides, azo compounds, etc. "Substantially free" means that the content of the polymerization initiator is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and more preferably less than 0.001 parts by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0265] When the resin composition of the present embodiment contains a curing accelerator, the lower limit of the content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. The curing accelerator may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0266] <Solvent> The resin composition of the present embodiment may contain a solvent, and preferably contains an organic solvent. When a solvent is contained, the resin composition of the present embodiment is in a form (solution or varnish) in which at least a part, preferably all, of the above-mentioned various resin solid contents are dissolved or compatible in the solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve or compatible at least a part, preferably all, of the above-mentioned various resin solid contents. Examples of polar organic solvents include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamides, etc.), and examples of non-polar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.). The solvent may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0267] <Other ingredients> In addition to the above components, the resin composition of the present embodiment may contain various polymeric compounds such as thermoplastic resins and their oligomers other than those described above, and various additives. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, defoamers, leveling agents, gloss agents, and polymerization inhibitors. These additives may be used alone or in combination of two or more. The resin composition of the present embodiment may be configured to be substantially free of a polymerization inhibitor. Substantially free means that the resin composition does not contain a polymerization inhibitor, or the content of the polymerization inhibitor in the resin composition is, for example, less than 0.008 parts by mass, preferably 0.007 parts by mass or less, more preferably 0.001 parts by mass or less, and even more preferably 0.0001 parts by mass or less, relative to 100 parts by mass of the resin solid content.

[0268] <Application> The resin composition of the present embodiment is used as a cured product. Specifically, the resin composition of the present embodiment can be suitably used as a material having low dielectric properties (Dk and / or Df), such as an insulating layer for a printed wiring board, a material for a semiconductor package, or a resin composition for electronic materials. The resin composition of the present embodiment can be suitably used as a material for a prepreg, a metal foil-clad laminate using a prepreg, a resin composite sheet, and a printed wiring board.

[0269] The resin composition of the present embodiment is used as a layered material (including film, sheet, etc.) such as a prepreg or a resin composite sheet that becomes an insulating layer of a printed wiring board, and when it is used as such a layered material, its thickness is preferably 5 μm or more, more preferably 10 μm or more. The upper limit of the thickness is preferably 200 μm or less, more preferably 180 μm or less. The thickness of the layered material means the thickness including the glass cloth, for example, when the resin composition of the present embodiment is impregnated into a glass cloth or the like. The material formed from the resin composition of the present embodiment may be used for applications in which a pattern is formed by exposure and development, or for applications in which no exposure and development is required. It is particularly suitable for applications in which no exposure and development is required.

[0270] <<Prepreg>> The prepreg of this embodiment is formed from a substrate (prepreg substrate) and the resin composition of this embodiment. The prepreg of this embodiment can be obtained, for example, by applying (for example, impregnating and / or coating) the resin composition of this embodiment to the substrate, and then semi-curing by heating (for example, a method of drying at 120 to 220°C for 2 to 15 minutes, etc.). In this case, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition (including the filler (D)) relative to the total amount of the semi-cured prepreg, is preferably in the range of 20 to 99% by mass, more preferably in the range of 20 to 80% by mass.

[0271] The substrate is not particularly limited as long as it is a substrate used in various printed wiring board materials. Examples of the substrate material include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, NER-glass, spherical glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), and organic fibers (e.g., polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. These substrates may be used alone or in combination of two or more. Among these substrates, from the viewpoint of dimensional stability, woven fabrics that have been subjected to ultra-opening treatment and clogging treatment are preferred, and from the viewpoint of strength and low water absorption, the substrate should have a thickness of 200 μm or less and a mass of 250 g / m 2 The following glass woven fabrics are preferred, and from the viewpoint of moisture absorption and heat resistance, glass woven fabrics that have been surface-treated with a silane coupling agent such as epoxy silane or amino silane are preferred. From the viewpoint of electrical properties, low dielectric glass cloths made of glass fibers exhibiting low dielectric properties (Dk and / or Df), such as L-glass, NE-glass, NER-glass, and Q-glass, are more preferred. An example of a substrate with a low relative dielectric constant is a substrate with a relative dielectric constant of 5.0 or less (preferably 3.0 to 4.9). An example of a substrate with a low dielectric loss tangent is a substrate with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative dielectric constant and the dielectric loss tangent are values ​​measured at a frequency of 10 GHz using a perturbation method cavity resonator.

[0272] <<Metal foil laminate>> The metal foil-clad laminate of this embodiment includes at least one layer formed from the prepreg of this embodiment and a metal foil disposed on one or both sides of the layer formed from the prepreg. The metal foil-clad laminate of this embodiment can be produced, for example, by disposing at least one prepreg of this embodiment (preferably two or more sheets are stacked), disposing a metal foil on one or both sides of the prepreg, and laminating and molding the laminate. More specifically, the laminate can be produced by disposing a metal foil such as copper or aluminum on one or both sides of the prepreg and laminating and molding the prepreg. The number of prepregs is preferably 1 to 10, more preferably 2 to 10, and even more preferably 2 to 9. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples of the metal foil include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited, and may be about 1.5 to 70 μm. In addition, when a copper foil is used as the metal foil, the copper foil is preferably adjusted to have a copper foil surface roughness Rz of 0.2 to 4.0 μm measured according to JIS B0601:2013. By setting the copper foil surface roughness Rz to 0.2 μm or more, the copper foil surface roughness becomes moderate, and the copper foil peel strength tends to be further improved. On the other hand, by setting the copper foil surface roughness Rz to 4.0 μm or less, the copper foil surface roughness becomes moderate, and the conductor loss tends to be further reduced. From the viewpoint of improving the peel strength, the copper foil surface roughness Rz is more preferably 0.5 μm or more, even more preferably 0.6 μm or more, and particularly preferably 0.7 μm or more, and from the viewpoint of reducing the conductor loss, it is more preferably 3.5 μm or less, even more preferably 3.0 μm or less, and particularly preferably 2.0 μm or less.

[0273] Examples of the lamination molding method include methods commonly used for molding laminates and multilayer boards for printed wiring boards. More specifically, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like is used to perform lamination molding at a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm. 2A method of laminating and molding the prepreg of this embodiment at a thickness of about 100 μm can be used. A multilayer board can also be produced by combining and laminating the prepreg of this embodiment and a separately prepared wiring board for an inner layer. As a method for producing a multilayer board, for example, a copper foil of about 35 μm is placed on both sides of one prepreg of this embodiment, and the laminate is formed by the above-mentioned molding method, and then an inner layer circuit is formed, and a blackening treatment is performed on this circuit to form an inner layer circuit board, and then the inner layer circuit board and the prepreg of this embodiment are alternately arranged one by one, and copper foil is further arranged on the outermost layer, and laminated and molded under the above-mentioned conditions, preferably under vacuum, to produce a multilayer board. The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.

[0274] As described above, the resin composition for electronic materials obtained using the resin composition of this embodiment (a resin composition consisting of a combination of specific components) can have excellent properties such as moldability of the resin composition, low dielectric properties (Dk and / or Df, particularly low dielectric tangent) of the cured product, low relative dielectric constant, crack resistance, appearance of the cured product, low thermal expansion, and moisture absorption and heat resistance.

[0275] <<Printed wiring board>> The printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the insulating layer includes at least one of a layer formed from the resin composition of the present embodiment and a layer formed from the prepreg of the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of a method for manufacturing a printed wiring board will be described. First, a metal foil-clad laminate such as the above-mentioned copper foil-clad laminate is prepared. Next, an etching treatment is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, and an inner layer substrate is manufactured. If necessary, a surface treatment is performed on the inner layer circuit surface of this inner layer substrate to increase the adhesive strength, and then a required number of the above-mentioned prepregs are stacked on the surface of the inner layer circuit, and a metal foil for an outer layer circuit is further stacked on the outside thereof, and the laminate is heated and pressed to form an integral body. In this way, a multi-layer laminate is manufactured in which an insulating layer made of a base material and a cured product of a resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, this multi-layer laminate is subjected to a hole drilling process for through holes and via holes, and then a plated metal coating is formed on the wall surface of the hole to provide electrical continuity between the inner layer circuit and the metal foil for the outer layer circuit. Furthermore, the metal foil for the outer layer circuit is etched to form the outer layer circuit, thereby producing a printed wiring board.

[0276] The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the above-mentioned resin composition of the present embodiment and / or its cured product. That is, the above-mentioned prepreg of the present embodiment (for example, a prepreg formed from a base material and the resin composition of the present embodiment impregnated or applied thereto) and the layer formed from the resin composition of the above-mentioned metal foil-clad laminate of the present embodiment are the insulating layer of the present embodiment. The present embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, refer to paragraphs 0200 to 0202 of JP 2021-021027 A, the contents of which are incorporated herein by reference.

[0277] In addition, it is preferable that the insulating layer formed of the cured product of the resin composition of this embodiment has a small surface roughness after roughening treatment. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness Ra is not particularly limited, but may be, for example, 10 nm or more. The arithmetic mean roughness Ra of the surface of the insulating layer is measured using a non-contact surface roughness meter in VSI mode with a 50x lens. The non-contact surface roughness meter used is WYKONT3300 manufactured by B-COIN Instruments.

[0278] <<Resin composite sheet>> The resin composite sheet of the present embodiment includes a support and a layer formed from the resin composition of the present embodiment arranged on the surface of the support. The resin composite sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin composite sheet is not particularly limited, but for example, a method of obtaining a resin composite sheet by applying (coating) a solution in which the resin composition of the present embodiment is dissolved in a solvent to a support and drying the solution can be mentioned.

[0279] Examples of the support used here include, but are not limited to, polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and release films obtained by applying a release agent to the surface of these films, organic film substrates such as polyimide film, conductive foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics), and other plate-shaped supports.

[0280] Examples of the application method (coating method) include a method in which a solution in which the resin composition of this embodiment is dissolved in a solvent is applied onto a support using a bar coater, a die coater, a doctor blade, a baker applicator, or the like. In addition, after drying, a single-layer sheet can be obtained by peeling or etching the support from a resin composite sheet in which the support and the resin composition are laminated. Note that a single-layer sheet can also be obtained without using a support by supplying a solution in which the resin composition of this embodiment is dissolved in a solvent into a mold having a sheet-shaped cavity and drying it to form it into a sheet.

[0281] In the preparation of the monolayer sheet or resin composite sheet of this embodiment, the drying conditions for removing the solvent are not particularly limited, but since low temperatures tend to leave the solvent in the resin composition, and high temperatures tend to promote curing of the resin composition, drying conditions of 20°C to 200°C for 1 to 90 minutes are preferred. The monolayer sheet or resin composite sheet can be used in an uncured state in which the solvent has simply been dried, or can be used in a semi-cured (B-stage) state as necessary. The thickness of the resin layer in the monolayer sheet or resin composite sheet of this embodiment can be adjusted by the concentration of the solution of the resin composition of this embodiment used for coating (coating) and the coating thickness, and is not particularly limited, but is preferably 0.1 to 500 μm, since the solvent tends to remain in the resin composition when the coating thickness is large. EXAMPLES

[0282] The present invention will be described in more detail below with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0283] <Measurement of weight average molecular weight and number average molecular weight> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin (T), hydroxy resin, and styrene resin were measured by gel permeation chromatography (GPC) using a liquid delivery pump (Shimadzu Corporation, LC-20AD), a differential refractive index detector (Shimadzu Corporation, RID-20A), and GPC columns (Showa Denko K.K., GPC KF-801, 802, 803, 804), tetrahydrofuran as the solvent, a flow rate of 1.0 mL / min, a column temperature of 40°C, and a calibration curve based on monodisperse polystyrene.

[0284] <Measurement of parameters α and β> The parameters α and β in the resin (resin (T)) represented by formula (T), hydroxy resin, and styrene resin are as follows: 1 The calculation was performed using H-NMR measurement. The synthesized resin was dissolved in a mixed solvent of heptane and methanol, and the process of drying was repeated to remove the residual solvent contained in the recovered solid. The recovered solid was then dissolved in CDCl3 and 1 H-NMR measurements were performed. 1 In H-NMR, the parameters α and β of each resin were calculated using the following formula.

number

[0285] Example 1 <Synthesis of resin (TA)> In a flask equipped with a thermometer and a condenser, 520 g of toluene, 0.75 g of activated clay, 150 g of 1,3-diisopropenylbenzene (Tokyo Chemical Industry Co., Ltd.), and a stirrer were placed and heated with stirring to an internal temperature of 50° C. The mixture was then gradually heated to an internal temperature of 70° C. over 6 hours and reacted at the internal temperature of 70° C. for an additional 1.2 hours. After cooling, the activated clay was removed by filtration, and the solvent was distilled off under heating and reduced pressure to obtain 125 g of a solid resin. The obtained resin (resin (TA)) represented by formula (T) had Mw of 1336, Mn of 713, Mw / Mn of 1.87, and in formula (Tx), the parameter α was 0.70, the parameter β was 0.92, and n+o+p was 3.5. In formula (Tx), the structures in parentheses represented by (a), (b), and (c) all had the same molecular weight, and n+o+p was calculated assuming that Mn of the synthesized resin was the average molecular weight (the same applies to the following examples and comparative examples). In addition, it was confirmed by GPC analysis that the residual monomer was 1% by mass or less. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0286] <Synthesis of hydroxy resin (A)> In a reactor equipped with a stirrer, thermometer, and cooling tube, 100 g of resin (TA), 400 g of toluene, 100 g of 2,6-xylenol, and 10 g of activated clay were placed and heated to an internal temperature of 70°C while stirring. The reaction was continued for an additional 5 hours at an internal temperature of 70°C. After cooling, the activated clay was removed by filtration, and the mixture was washed twice with a 1M aqueous solution of sodium hydroxide to remove the remaining 2,6-xylenol. Washing with pure water was repeated until the pH was neutral, and then the solvent was distilled off under reduced pressure with heating to obtain a solid resin. The resulting resin (hydroxy resin (A)) represented by the formula (T-OH) had an Mw of 1604, an Mn of 1090, an Mw / Mn of 1.47, and in the formula (Tx-OH), n+o+p was 4.3 and the OH equivalent was 571 g / eq. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0287] The OH equivalent (hydroxyl group equivalent) of the hydroxy resin was measured according to the following method (the same applies to the following Examples and Comparative Examples). The hydroxyl group equivalent was determined by adding a 10% by volume solution of acetic anhydride in pyridine to the hydroxyl resin, reacting the hydroxyl resin with acetic anhydride in an oil bath at 100°C, then adding water to react the unreacted acetic anhydride with the water, titrating with sodium hydroxide to determine the amount of acetic acid in the system, and calculating the reaction amount of acetic anhydride and hydroxyl resin, which was determined as the mass of hydroxyl resin per mole of hydroxyl groups.

[0288] <Synthesis of styrene resin (A)> In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (A) obtained above, 400 g of toluene, 29.40 g (0.193 mol) of vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-14"), 22.58 g (0.07 mol) of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 66.0 g of pure water, and 84.1 g of a 25% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The resulting solution was concentrated and dropped into methanol to solidify, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and dried in vacuum to obtain a solid resin. The obtained resin (styrene resin (A)) represented by formula (T-St) had Mw of 1800, Mn of 1320, Mw / Mn of 1.36, and in formula (Tx-St), n+o+p was 4.3, the OH equivalent was 25500 g / eq., and the total amount of total Cl and total Br was 250 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0289] The total chlorine atom concentration (total Cl) and the total bromine atom concentration (total Br) of the styrene resin were measured using an ion chromatography with a combustion device (combustion / absorption section device: AQF-2100H manufactured by Mitsubishi Chemical Analytech, ion chromatography device: Dionex Integrion CT manufactured by Thermo Fisher Scientific) (the same applies to the following Examples and Comparative Examples). In this reaction system, no materials other than those specified were added (the same applies to the following Examples and Comparative Examples).

[0290] The OH equivalent (hydroxyl group equivalent) [g / eq.] of the styrene resin was measured according to the following method (the same applies to the following Examples and Comparative Examples). The styrene resin powder was weighed and the mass was recorded. This powder was placed in a measuring flask, and then the flask was filled up to a specified amount with dichloromethane to prepare a sample liquid for measurement (measurement sample). This sample liquid was placed in a measurement cell and set in an infrared spectrophotometer (FT / IR-4600, manufactured by JASCO Corporation). Infrared spectroscopy of the sample liquid was performed, and -1 The area of ​​the spectrum peak near the peak was recorded. The hydroxyl group concentration [mol / L] was calculated from this area value and the calibration curve. Subsequently, the hydroxyl group equivalent was calculated according to the following formula. Hydroxyl equivalent [g / eq.] = powder mass in measurement sample [g] / hydroxyl concentration [mol / L] × measurement sample liquid volume [L]

[0291] <Physical Properties>

[0292] <<Manufacture of hardened plate test pieces with a thickness of 1.0 mm>> 4.5 g of the obtained styrene resin powder was spread in a stainless steel mold frame measuring 100 mm x 30 mm x 1.0 mm high, set in a vacuum press (Kitagawa Seiki Co., Ltd.), held at 200°C for 1.5 hours, and pressed at a surface pressure of 1.9 MPa to produce a hardened plate. The glass transition temperature, dielectric constant (Dk), and dielectric loss tangent (Df) of the cured sheet were evaluated. The evaluation results are shown in Table 1.

[0293] <<Measurement and evaluation methods>> (1) Glass transition temperature The cured plate was downsized to a size of 12.7 mm x 30 mm, and the cured plate was subjected to measurement by a dynamic mechanical analysis (DMA) bending method in accordance with JIS C6481 5.17.2 using a dynamic viscoelasticity measuring device, and the peak temperature of the loss modulus was determined as the glass transition temperature. The unit was °C. The dynamic viscoelasticity measuring device used was a DMA Q800 manufactured by TA Instruments Co., Ltd.

[0294] (2) Dielectric constant (Dk) and dielectric loss tangent (Df) The cured plate was downsized to a width of 1.0 mm, and then dried at 120°C for 60 minutes. The relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying were measured at a frequency of 10 GHz using a perturbation method cavity resonator. The measurement temperature was 23°C. The perturbation method cavity resonator used was Agilent8722ES manufactured by Agilent Technologies.

[0295] Example 2 <Synthesis of resin (TB)> In a flask equipped with a thermometer and a condenser, 520 g of toluene, 0.75 g of activated clay, 150 g of 1,3-diisopropenylbenzene (Tokyo Chemical Industry Co., Ltd.), and a stirrer were placed and heated with stirring to an internal temperature of 50° C. The mixture was then gradually heated to an internal temperature of 70° C. over 5 hours and reacted at the internal temperature of 70° C. for an additional hour. After cooling, the activated clay was removed by filtration, and the solvent was distilled off under heating and reduced pressure to obtain 129 g of a solid resin. The resulting resin (resin (TB)) represented by formula (T) had an Mw of 1193, an Mn of 693, and an Mw / Mn of 1.72, and in formula (Tx), the parameter α was 0.63, the parameter β was 1.07, and n+o+p was 3.4. GPC analysis confirmed that the residual monomer was 1% by mass or less. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0296] <Synthesis of hydroxy resin (B)> Hydroxy resin (B) was obtained in the same manner as in Example 1 <Synthesis of hydroxy resin (A)>, except that resin (TA) was changed to resin (TB) and the reaction temperature was changed to 110°C. The resulting resin (hydroxy resin (B)) represented by the formula (T-OH) had an Mw of 1730, an Mn of 1290, and an Mw / Mn of 1.34. In the formula (Tx-OH), the parameter α was 0.92, n+o+p was 5.6, and the OH equivalent was 671 g / eq.

[0297] <Synthesis of styrene resin (B)> In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (B) obtained above, 400 g of toluene, 25.02 g (0.164 mol) of vinylbenzyl chloride (AGC Seimi Chemical Co., Ltd., "CMS-14"), 19.22 g (0.06 mol) of tetrabutylammonium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.), 56.2 g of pure water, and 71.5 g of 25% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1 M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The obtained solution was concentrated and dropped into methanol to solidify, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and vacuum dried to obtain a solid resin. The obtained resin (styrene resin (B)) represented by formula (T-St) had an Mw of 2060, an Mn of 1520, and an Mw / Mn of 1.36. In formula (Tx-St), n+o+p was 5.6, the OH equivalent was 72600 g / eq., and the total amount of total Cl and total Br was 320 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0298] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0299] Example 3 <Synthesis of hydroxy resin (C)> Hydroxy resin (C) was obtained in the same manner as in Example 1 <Synthesis of hydroxy resin (A)>, except that resin (TA) was changed to resin (TB). The resulting resin (hydroxy resin (C)) represented by the formula (T-OH) had an Mw of 1551, an Mn of 1105, and an Mw / Mn of 1.40. In the formula (Tx-OH), the parameter α was 0.90, n+o+p was 4.4, and the OH equivalent was 556 g / eq.

[0300] <Synthesis of styrene resin (C)> In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (C) obtained above, 400 g of toluene, 30.20 g (0.198 mol) of vinylbenzyl chloride (AGC Seimi Chemical Co., Ltd., "CMS-14"), 23.19 g (0.07 mol) of tetrabutylammonium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.), 67.8 g of pure water, and 86.3 g of 25% by mass NaOH aqueous solution were charged and stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The resulting solution was concentrated and dropped into methanol to solidify, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and vacuum dried to obtain a solid resin. The obtained resin (styrene resin (C)) represented by formula (T-St) had Mw of 1820, Mn of 1330, and Mw / Mn of 1.37. In formula (Tx-St), the parameter α was 0.90, n+o+p was 4.4, the OH equivalent was 84600 g / eq., and the total amount of total Cl and total Br was 200 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0301] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0302] Example 4 <Synthesis of hydroxy resin (D)> Hydroxy resin (D) was obtained in the same manner as in Example 1 <Synthesis of hydroxy resin (A)>, except that resin (TA) was changed to resin (TB), the reaction solvent was changed from toluene to chlorobenzene, and the reaction temperature was changed to 130°C. The resulting resin (hydroxy resin (D)) represented by the formula (T-OH) had an Mw of 1945, an Mn of 1368, and an Mw / Mn of 1.42. In the formula (Tx-OH), the parameter α was 0.90, n+o+p was 6.1, and the OH equivalent was 690 g / eq.

[0303] <Synthesis of styrene resin (D)> In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (D) obtained above, 400 g of toluene, 24.33 g (0.159 mol) of vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-14"), 18.69 g (0.06 mol) of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 54.7 g of pure water, and 69.6 g of a 25% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1 M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The resulting solution was concentrated and dropped into methanol to be solidified, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and vacuum dried to obtain a solid resin. The obtained resin (hydroxy resin (D)) represented by formula (T-St) had an Mw of 2,270, an Mn of 1,600, and an Mw / Mn of 1.42. In formula (Tx-St), the parameter α was 0.91, n+o+p was 6.1, the OH equivalent was 76,200 g / eq., and the total amount of total Cl and total Br was 220 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0304] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0305] Example 5 <Synthesis of resin (TE)> In a three-neck flask equipped with a thermometer and a cooling tube, 520 g of toluene, 3 g of activated clay, and a stirrer were placed and heated to an internal temperature of 70°C while stirring. Then, 150 g of 1,3-diisopropenylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while controlling the dropping speed so that the internal temperature did not exceed 80°C. After dropping, the mixture was stirred until the internal temperature decreased to 70°C, and 150 g of 1,3-diisopropenylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was similarly added dropwise, and the mixture was allowed to react for 2 hours after the end of the dropping. At the end of the reaction, 433 g of toluene was added, and the activated clay was removed by filtration. The filtrate was heated under reduced pressure to distill off the solvent, obtaining 231 g of a solid resin. The resulting resin (resin (TE)) represented by formula (T) had an Mw of 2674, an Mn of 1153, and an Mw / Mn of 2.32, and in formula (Tx), the parameter α was 0.71, the parameter β was 0.50, and n+o+p was 6.3. GPC analysis confirmed that the residual monomer was 1% by mass or less.

[0306] <Synthesis of hydroxy resin (E)> The same procedure was carried out as in Example 1 <Synthesis of Hydroxy Resin (A)>, except that resin (TA) was changed to resin (TE), the reaction solvent was changed from toluene to chlorobenzene, and the reaction temperature was changed to 130°C, to obtain Hydroxy Resin (E). The resulting resin (hydroxy resin (E)) represented by the formula (T-OH) had an Mw of 2229, an Mn of 1411, an Mw / Mn of 1.58, and in the formula (Tx-OH), n+o+p was 6.4 and the OH equivalent was 860 g / eq.

[0307] <Synthesis of styrene resin (E)> In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (E) obtained above, 400 g of toluene, 19.52 g (0.128 mol) of vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-14"), 14.99 g (0.05 mol) of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 43.9 g of pure water, and 55.8 g of 25% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1 M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The obtained solution was concentrated and dropped into methanol to be solidified, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and dried in vacuum to obtain a solid resin. The obtained resin (styrene resin (E)) represented by formula (T-St) had an Mw of 2360, an Mn of 1650, and an Mw / Mn of 1.43. In formula (Tx-St), n+o+p was 6.4, the OH equivalent was 55600 g / eq., and the total amount of total Cl and total Br was 240 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0308] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0309] Comparative Example 1 <Synthesis of hydroxy resin (F)> The synthesis was carried out as follows according to Example 1 of JP-A-6-172242. A 2-liter, four-necked round-bottom flask equipped with a thermometer, stirrer, reflux condenser and drain was charged with 549.0 g (4.5 mol) of 2,6-xylenol, 291.0 g (1.5 mol) of m-bis(α-hydroxyisopropyl)benzene, 840 g of toluene and 84 g of acid clay (montmorillonite K10), and heated to 110°C for 8 hours while removing water by azeotropy. The mixture was concentrated under reduced pressure with heating to remove the volatiles, then diluted with toluene and filtered to remove the acid clay. The filtrate was collected and concentrated under reduced pressure with heating to obtain a resinous solid. The resulting resin (hydroxy resin (F)) had an Mw of 920, an Mn of 770, an Mw / Mn of 1.19, and in the formula (Tx-OH), n+o+p was 2.3 and the OH equivalent was 360 g / eq. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0310] <Synthesis of styrene resin (F)> The synthesis was carried out as follows according to Example 3 of JP-A-6-172242. In a 2-liter, four-necked round-bottom flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping funnel, 90.0 g (0.25 moleq) of the hydroxy resin (F) obtained above, 150 ml of dimethyl sulfoxide, and 150 ml of tetrahydrofuran were charged and dissolved at 40°C. 10.4 g (0.26 moleq) of powdered NaOH and 161 mg of methylhydroquinone were added and stirred at 40°C for 1 hour. While maintaining the temperature at 40°C, 39.7 g (0.26 moleq) of p-chloromethylstyrene (trade name CMS-14, manufactured by Seimi Chemical Co., Ltd.) was added dropwise over 1 hour, and the temperature was raised to 80°C and kept at that temperature for 14 hours. The reaction solution was diluted with 300 g of toluene, filtered, and the salt was removed, followed by washing with water, and the organic layer was dried over anhydrous sodium sulfate. The salt was removed by filtration, and the solution was concentrated under reduced pressure with heating to obtain a resinous product. The resulting resin (styrene resin (F)) had an Mw of 1150, an Mn of 995, an Mw / Mn of 1.16, and in the formula (Tx-St), n+o+p was 2.3, an OH equivalent was 27200 g / eq., and the total amount of total Cl and total Br was 3850 ppm by mass.

[0311] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0312] Comparative Example 2 <Synthesis of styrene resin (G)> The styrene resin (F) obtained in Comparative Example 1 was dissolved in heptane, dropped into methanol to solidify, low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was recovered by filtration and dried in vacuum to obtain a solid resin (styrene resin (G)). The resulting resin (styrene resin (G)) had an Mw of 1170, an Mn of 1005, an Mw / Mn of 1.16, and in the formula (Tx-St), n+o+p was 2.3, an OH equivalent was 27500 g / eq., and the total amount of total Cl and total Br was 470 ppm by mass.

[0313] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0314] [Table 1]

[0315] Fig. 1 shows an NMR chart of the hydroxy resin (C) synthesized in Example 3. Fig. 2 shows an NMR chart of the styrene resin (C) synthesized in Example 3. Fig. 3 shows a GPC chart of the styrene resin (C) synthesized in Example 3.

[0316] Example 6 <Synthesis of hydroxy resin (F)> In a reactor equipped with a stirrer, thermometer, and cooling tube, 100 g of resin (TB), 400 g of chlorobenzene, 100 g of phenol, and 10 g of activated clay were placed and heated to an internal temperature of 130°C while stirring. The reaction was continued for another 3 hours at an internal temperature of 130°C. After cooling, the activated clay was removed by filtration, and the mixture was washed twice with a 1M aqueous solution of sodium hydroxide to remove the remaining phenol. Washing with pure water was repeated until the pH became neutral, and then the solvent was distilled off under reduced pressure with heating to obtain a solid resin. The obtained resin represented by formula (T-1-OH) (resin represented by formula (T-OH), hydroxy resin (F)) had an Mw of 2100, an Mn of 1355, a parameter α of 0.86, an Mw / Mn of 1.55, and in formula (Tx-OH), n+o+p was 6.4, and an OH equivalent of 680 g / eq. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0317] In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (F) obtained above, 400 g of toluene, 24.69 g (0.162 mol) of vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-14"), 18.96 g (0.06 mol) of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 56 g of pure water, and 71 g of a 25% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The resulting solution was concentrated and dropped into methanol to solidify, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and vacuum dried to obtain a solid resin. The obtained resin represented by formula (T-1-St) (resin represented by formula (T-St), styrene resin (F)) had Mw of 2300, Mn of 1600, and Mw / Mn of 1.44. In formula (Tx-St), the parameter α was 0.88, n+o+p was 6.5, the OH equivalent was 28500 g / eq., and the total amount of total Cl and total Br was 170 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0318] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0319] Example 7 <Synthesis of hydroxy resin (G)> In a reactor equipped with a stirrer, thermometer, and cooling tube, 100g of resin (TB), 400g of chlorobenzene, 122g of 2-benzylphenol, and 40g of activated clay were placed and heated to an internal temperature of 130°C while stirring. The reaction was continued for another 3 hours at an internal temperature of 130°C. After cooling, the activated clay was removed by filtration, and the mixture was washed twice with a 1M aqueous solution of sodium hydroxide to remove the remaining phenol. Washing with pure water was repeated until the pH became neutral, and then the solvent was distilled off under reduced pressure with heating to obtain a solid resin. The obtained resin represented by formula (T-1-OH) (resin represented by formula (T-OH), hydroxy resin (G)) had an Mw of 2110, an Mn of 1120, and an Mw / Mn of 1.88, and in formula (Tx-OH), n+o+p was 3.8, and the OH equivalent was 560 g / eq. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0320] In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 100 g of the hydroxy resin (G) obtained above, 400 g of toluene, 29.98 g (0.196 mol) of vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd., "CMS-14"), 23.03 g (0.07 mol) of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 67 g of pure water, and 86 g of 25% by mass NaOH aqueous solution were charged, and the mixture was stirred at a reaction temperature of 70°C. After stirring for 5 hours, the organic layer was washed with a 1 M aqueous hydrochloric acid solution and then with pure water until the pH became 7. The obtained solution was concentrated and dropped into methanol to solidify, and low molecular weight compounds (compounds with a molecular weight of 400 or less) containing chlorine atoms and / or bromine atoms were removed, and the solid was collected by filtration and dried in vacuum to obtain a solid resin. The obtained resin represented by formula (T-1-St) (resin represented by formula (T-St), styrene resin (G)) had Mw of 2350, Mn of 1370, and Mw / Mn of 1.72. In formula (Tx-St), the parameter α was 0.86, n+o+p was 3.9, the OH equivalent was 39600 g / eq., and the total amount of total Cl and total Br was 320 ppm by mass. Mn and Mw were measured according to the above method. The number of repeating units was calculated from the Mn value.

[0321] <Physical Properties> The physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0322] [Table 2]

Claims

1. A hydroxy resin represented by the formula (T-OH) and having a number average molecular weight of 850 to 4,000. 【Chemistry 1】 (In formula (T-OH), R is a group containing a structural unit represented by formula (Tx-OH). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y is independently an integer of 0 to 4.) 【Chemistry 2】 (In formula (Tx-OH), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p are each independently a number from 0 to 20, and 1.0≦n+o+p≦20.

0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x is an integer from 0 to 4. It is bonded to the structural unit (a), (b), or (c), or to another group, and each structural unit may be bonded randomly.)

2. 2. The hydroxy resin of claim 1, wherein the number average molecular weight is from 900 to 2500.

3. The hydroxy resin according to claim 1 or 2, wherein the formula (T-OH) is represented by the formula (T-OH2): 【Chemistry 3】 (In formula (T-OH2), R is a group containing a structural unit represented by formula (Tx-OH). Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y independently represent an integer of 0 to 4.) 【Chemistry 4】 (In formula (Tx-OH), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p are each independently a number from 0 to 20, and 1.0≦n+o+p≦20.

0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x is an integer from 0 to 4. It is bonded to the structural unit (a), (b), or (c), or to another group, and each structural unit may be bonded randomly.)

4. A styrene resin represented by the formula (T-St) and having a number average molecular weight of 1,050 to 4,000. 【Chemistry 5】 (In formula (T-St), R is a group containing a structural unit represented by formula (Tx-St). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each Mc is independently a hydrocarbon group having 1 to 12 carbon atoms. Each x, y, and z is independently an integer of 0 to 4. r is an integer of 1 to 6. R １ , R ２ , and R ３ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. 【Chemistry 6】 (In formula (Tx-St), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p each independently are a number from 0 to 20, and 1.0≦n+o+p≦20.

0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural unit (a), (b), or (c), or to another group, and each structural unit may be bonded randomly.)

5. The styrene resin according to claim 4, wherein the formula (T-St) is represented by the formula (T-St2): 【Chemistry 7】 (In formula (T-St2), R is a group containing a structural unit represented by formula (Tx-St). Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each Mc independently represents a hydrocarbon group having 1 to 12 carbon atoms. Each x, y, and z independently represent an integer of 0 to 4. r represents an integer of 1 to 6. R １ , R ２ , and R ３ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. 【Chemistry 8】 (In formula (Tx-St), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p each independently are a number from 0 to 20, and 1.0≦n+o+p≦20.

0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural unit (a), (b), or (c), or to another group, and each structural unit may be bonded randomly.)

6. The styrene resin according to claim 4 or 5, wherein the number average molecular weight is 1050 to 2500.

7. The styrene resin according to claim 4 or 5, wherein the sum of the total chlorine content and the total bromine content is 2,500 ppm by mass or less.

8. The styrene resin according to claim 4 or 5, wherein a cured product of the styrene resin has a dielectric loss tangent of 0.0030 or less at a frequency of 10 GHz.

9. The resin (T) is used, The resin (T) is a resin represented by the formula (T): The method for producing the hydroxy resin according to claim 1 or 2. 【Chemistry 9】 (In formula (T), R is a group containing a structural unit represented by formula (Tx). Ma represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer of 0 to 4.) 【Chemistry 10】 (In formula (Tx), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p each independently are a number from 0 to 20, and 1.0≦n+o+p≦20.

0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x represents an integer from 0 to 4. It is bonded to the structural unit (a), (b), or (c), or to another group, and each structural unit may be bonded randomly.)

10. A method for producing a hydroxy resin according to claim 9, comprising reacting the resin (T) with a compound represented by formula (P). 【Chemistry 11】 (In formula (P), each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. y is an integer of 0 to 4.)

11. The method for producing a hydroxy resin according to claim 10, wherein the compound represented by formula (P) includes a compound represented by formula (P1). 【Chemistry 12】 (In formula (P1), each Mb independently represents a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom; and y represents an integer of 0 to 4.)

12. The method for producing a hydroxy resin according to claim 10, wherein the total content of m-bis(α-hydroxyisopropyl)benzene, p-bis(α-hydroxyisopropyl)benzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene in the reaction system when the compound represented by formula (P) is reacted with the resin (T) is 10 mass% or less based on the amount of the resin (T).

13. The method for producing a styrene resin according to claim 4 or 5, comprising using a hydroxy resin represented by the formula (T-OH) and having a number average molecular weight of 850 to 4000. 【Chemistry 13】 (In formula (T-OH), R is a group containing a structural unit represented by formula (Tx-OH). Each Arm is independently a benzene ring, a naphthalene ring, or an anthracene ring. Each Ma is independently a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Each Mb is independently a hydroxyl group, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group or a halogen atom. Each x and y is independently an integer of 0 to 4.) 【Chemistry 14】 (In formula (Tx-OH), n, o, and p are the average number of repeating units, n is a number greater than 0 and equal to or less than 20, o and p are each independently a number from 0 to 20, and 1.0≦n+o+p≦20.

0. Each Ma independently represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x is an integer from 0 to 4. It is bonded to the structural unit (a), (b), or (c), or to another group, and each structural unit may be bonded randomly.)

14. The method for producing a styrene resin according to claim 13, comprising reacting the hydroxy resin with a compound represented by formula (S). 【Chemistry 15】 (In formula (S), Hr represents a chlorine atom or a bromine atom. Mc represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6. R １ , R ２ , and R ３ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.

15. A resin composition comprising the styrene resin according to claim 4 or 5.

16. A cured product of the resin composition according to claim 15.

17. A prepreg formed from a substrate and the resin composition according to claim 15.

18. 20. A metal foil clad laminate comprising at least one layer formed from the prepreg according to claim 17 and metal foil disposed on one or both sides of the layer formed from the prepreg.

19. A resin composite sheet comprising a support and a layer formed from the resin composition according to claim 15, which is disposed on a surface of the support.

20. A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, the insulating layer comprising a layer formed from the resin composition according to claim 15.

21. A semiconductor device comprising the printed wiring board according to claim 20.

Images